JP5038561B2 - Use of ammonia-free polymer dispersions, polymer powders and polymer granules as admixtures for inorganic building materials, methods for improving such building materials and their mechanical strength - Google Patents

Description

【００４２】
〔式中、Ｒ^１ およびＲ^２ は水素またはＣ_４ 〜Ｃ_２４−アルキルを表し、かつ同時には水素でなく、またＸおよびＹはアルカリ金属イオンおよび／またはアンモニウムイオンであることができる〕の化合物も挙げられる。ＸおよびＹは有利にはナトリウム、カリウムまたはアンモニウムであり、その際ナトリウムが殊に有利である。しばしば、モノアルキル化製品の５０〜９０質量％の割合を有する工業的混合物、例えばダウファックス(Dowfax)^（Ｒ） ２Ａ１（ダウ・ケミカル社(Dow Chemical Company)の商品名）も使用される。化合物Ｉは、一般に、例えば米国特許（ＵＳ−Ａ）第４２６９７４９号明細書から公知であり、また市場で入手できる。
【００４３】
本発明による使用のために有利には、アルコキシル化乳化剤、殊には非イオン性アルコキシル化乳化剤および／または陰イオン性アルコキシル化乳化剤を含むポリマー分散液である。アルコキシル化乳化剤は本発明により使用されるコポリマーの取り扱い性、例えばコポリマーおよび水硬性結合剤の混合性および加工性およびポリマーと水硬性結合剤との許容性も、コポリマーを用いて変性された水硬性結合剤の取り扱い性および機械的性質も改善する。
【００４４】
アルコキシル化乳化剤は、親水性部分内にオリゴアルキレンオキシド単位またはポリアルキレンオキシド単位を有する乳化剤である。通常、アルコキシル化乳化剤は、親油性基を有する親油性化合物または複数の化合物をアルキレンオキシド、殊にはエチレンオキシドおよび／またはプロピレンオキシドと反応させて得られる。このようなアルコキシル化乳化剤は、追加してイオン性殊には陰イオン性基を用いて変性されていてもよい。これに応じて、少なくとも１個の陰イオン性または陰イオン原性基を有する陰イオン性アルコキシル化乳化剤と、このような基を持っていない非イオン性アルコキシル化乳化剤が区別される。
【００４５】
親油性基を有する親油性化合物または複数の化合物の例は、脂肪族、芳香族および／または芳香脂肪族アルコール、アミド、アミンおよびカルボン酸ならびにこれらの誘導体である。有利には、親油性基を有する親油性化合物または複数の化合物は、脂肪酸、脂肪アルコール、オキソアルコール、これらから誘導されたアミン、アミドおよび塩、フェノール、アルキルフェノール、ヒドロキシナフタレンまたはアミノナフタレン、ジカルボン酸およびこれらのエステルまたは半エステルおよび少なくとも１個のヒドロキシル基を有する親油性または親油性部分を有するポリアルキレンオキシド、例えばポリプロピレンオキシド、ポリブチレンオキシドおよびエチレンオキシド、プロピレンオキシドおよび／またはブチレンオキシドから成るランダム共重合体またはブロック共重合体である。
【００４６】
このようなアルコキシル化乳化剤のアルコキシル化度は、通常、２〜１５０、有利には３〜１００および殊に有利には４〜５０の範囲内にある。
【００４７】
有利な非イオン性脂肪族アルコキシル化乳化剤の例は、アルコキシル化度３〜１００、有利には４〜５０を有するエトキシル化またはエトキシル化／プロポキシル化、有利にはエトキシル化Ｃ_６ 〜Ｃ_３２−脂肪アルコールおよびＣ_６ 〜Ｃ_３２−脂肪アミン、Ｃ_６ 〜Ｃ_６０−オキソアルコールおよびＣ_６ 〜Ｃ_６０−アミン、線状第一級Ｃ_６ 〜Ｃ_６０−チーグラー(Ziegler) アルコール、脂肪酸アルキロールアミド、脂肪酸および脂肪酸アミドならびにポリアルキレンオキシド付加物、例えばエチレンオキシド−プロピレンオキシド−ブロック共重合体である。
【００４８】
有利な非イオン性脂肪族アルコキシル化乳化剤は、エトキシル化Ｃ_６ 〜Ｃ_３２−脂肪アルコール、有利にはＣ_８ 〜Ｃ_２０−脂肪アルコール、殊にはＣ_９ 〜Ｃ_１６−脂肪アルコール、例えば天然産出脂肪酸の還元により得られるほとんど分枝していない脂肪アルコール、および脂肪アルコールと比較して一般にさらに多く分枝しているエトキシル化Ｃ_６ 〜Ｃ_３２−オキソアルコール、有利にはＣ_８ 〜Ｃ_２０−オキソアルコールおよび殊にはＣ_９ 〜Ｃ_１６−オキソアルコールであって、平均エトキシル化度２〜１５０、有利には４〜５０、殊には６〜３０、例えば８〜１５または１２〜２５のものから選ばれる。有利な非イオン性脂肪族アルコキシル化乳化剤の例は、エトキシル化度４〜５０、殊には８〜２５を有するエトキシル化ラウリルアルコール、例えばＢＡＳＦ株式会社のルテンゾル商標(Lutensolmarken)のＬＵＴＥＮＳＯＬ^（Ｒ） ＡＴ１８およびＡＴ２５である。
【００４９】
非イオン性芳香族または芳香−脂肪族アルコキシル化乳化剤の例は、平均アルコキシル化度２〜１５０、有利には３〜１００および殊には３〜５０を有するエトキシル化およびエトキシル化／プロポキシル化、有利にはエトキシル化Ｃ_６ 〜Ｃ_３２−アルキルフェノール、殊にはＣ_６ 〜Ｃ_１６−アルキルフェノールである。
【００５０】
陰イオン性アルコキシル化乳化剤の陰イオン基は、通常、硫酸基、スルホン酸基、カルボン酸基、ホスホン酸基およびリン酸基から選ばれる。陰イオン基の対イオンとして好適には、陽イオン、例えばナトリウムイオン、カリウムイオン、カルシウムイオンまたはアンモニウムイオンならびにこれらの混合物である。有利には、アンモニウムイオンとは異なる対イオンは、軽度に揮発性のアミン、例えばアンモニア、メチルアミンまたはエチルアミンである、有利な対イオンはナトリウムイオンである。有利な陰イオン基は、硫酸基およびスルホン酸基である。
【００５１】
陰イオン性アルコキシル化乳化剤の例は、上記の非イオン性アルコキシル化乳化剤の硫酸半エステルおよびリン酸モノエステル、ならびにＣ_８ 〜Ｃ_３２−アルケニルポリエトキシスルホナートならびにＣ_８ 〜Ｃ_３２−アルケニルポリエトキシスルファート、Ｃ_８ 〜Ｃ_３２−アルキルグリセリルポリエトキシスルホナート、エトキシル化スルホコハク酸半エステルおよびエトキシル化スルホコハク酸ジエステル、Ｃ_８ 〜Ｃ_３２−アルケニルポリエトキシホスファートまたはジアルキルポリエトキシホスファート、エトキシル化され一回または複数回核スルホン化されたモノアルキルビフェニルエーテルおよびジアルキルビフェニルエーテル、エトキシル化α−スルホ脂肪酸エステル、エトキシル化脂肪酸アルカノールアミンスルファート、スルホン化または硫酸化エトキシル化脂肪酸エステル、脂肪酸サルコシド、脂肪酸グリコラート、脂肪酸ラクタート、脂肪酸タウリドおよび脂肪酸イソチオナートであって、これらは２〜１５０、有利には２〜１００および殊に有利には３〜５０の範囲内のアルコキシル化度を有し、およびこれらの塩、殊にはアルカリ金属塩、例えばナトリウム塩またはカリウム塩、またはアンモニウム塩、有機アミン、例えばモノ−Ｃ_１ 〜Ｃ_４ −アルキルアミン、ジ−Ｃ_１ 〜Ｃ_４ −アルキルアミンまたはトリ−Ｃ_１ 〜Ｃ_４ −アルキルアミンまたはモノエタノールアミン、ジエタノールアミンまたはトリエタノールアミンとの塩である。
【００５２】
有利な陰イオン性脂肪族アルコキシル化乳化剤は、エトキシル化Ｃ_８ 〜Ｃ_２０−脂肪アルコール、殊にはＣ_９ 〜Ｃ_１６−脂肪アルコール、例えば天然産出脂肪酸の還元により得られるほとんど分枝していない脂肪アルコールの硫酸半エステル、および一般に脂肪アルコールと比較してより多く分枝しているエトキシル化Ｃ_８ 〜Ｃ_３２−オキソアルコール、殊にはＣ_９ 〜Ｃ_１６−オキソアルコールであって、平均エトキシル化度２〜５０、殊には２〜３０、例えば２〜１５または９〜３０を有するものから選ばれる。
【００５３】
有利な陰イオン性芳香族または陰イオン性芳香−脂肪族アルコキシル化乳化剤は、エトキシル化およびエトキシル化／プロポキシル化、有利にはエトキシル化Ｃ_６ 〜Ｃ_３２−アルキルフェノール、殊にはＣ_６ 〜Ｃ_１６−アルキルフェノールおよび殊に有利にはオクチルフェノールおよびノニルフェノールの硫酸−半エステルであって、２〜５０、殊には２〜３５の範囲内の平均アルコキシル化度を有するものから選ばれる。
【００５４】
場合により、本発明による調製物は、非アルコキシル化乳化剤も含むことができるが、しかし通常、使用される乳化剤の少なくとも５０質量％、有利には少なくとも７５質量％はアルコキシル化乳化剤である。一つの態様形では、本発明による調製物は、実質的に非アルコキシル化乳化剤を含まない。他の有利な態様形は、少なくとも１種の非イオン性アルコキシル化乳化剤およびアルコキシル化および陰イオン性非アルコキシル化乳化剤から選ばれた少なくとも１種の陰イオン性乳化剤を含む調製物に関する。
【００５５】
有利には、本発明により使用されるポリマー分散液またはこれから乾燥により、すなわち揮発性成分の少なくとも８０質量％、有利には少なくとも８５質量％または少なくとも９０質量％を除去することにより得られるポリマー粉末またはポリマー顆粒は、ポリマー分に対して０．２〜１０質量％および有利には０．５〜５質量％の少なくとも１種の乳化剤を含む。
【００５６】
本発明の有利な態様形では、アルコキシル化乳化剤として、少なくとも１種の非イオン性アルコキシル化乳化剤、有利には非イオン性脂肪族アルコキシル化乳化剤を使用する。
【００５７】
有利には、本発明により使用される重合体は、
−少なくとも１種の非イオン性アルコキシル化乳化剤および少なくとも１種の陰イオン性アルコキシル化乳化剤の混合物または
−少なくとも１種の非イオン性アルコキシル化乳化剤、少なくとも１種の陰イオン性アルコキシル化乳化剤および少なくとも１種の陰イオン性非アルコキシル化乳化剤の混合物または
−少なくとも１種の陰イオン性非アルコキシル化乳化剤および少なくとも１種の非イオン性アルコキシル化乳化剤の混合物
を含む。
【００５８】
このような乳化剤の混合物を含むポリマー分散液は、殊にはせん断負荷に対するさらに上昇した安定性を特徴とする。
【００５９】
本発明により使用される共重合体が、少なくとも１種の陰イオン性乳化剤および少なくとも１種の非イオン性アルコキシル化乳化剤の混合物を含む場合には、含まれている乳化剤の全量の通常は１５〜９０質量％、有利には２５〜８０質量％および殊には４０〜７０質量％が陰イオン性乳化剤に割り当てられる。
【００６０】
本発明による殊に有利な乳化剤混合物は、少なくとも１種の非イオン性脂肪族アルコキシル化乳化剤、有利にはエトキシル化Ｃ_８ 〜Ｃ_２０−脂肪アルコール、殊にはＣ_９ 〜Ｃ_１６−脂肪アルコール、および／またはエトキシル化Ｃ_８ 〜Ｃ_３２−オキソアルコール、殊にはＣ_９ 〜Ｃ_１６−オキソアルコールであって、平均エトキシル化度５〜５０、殊には６〜３０を有するもの、および少なくとも１種の陰イオン性脂肪族アルコキシル化乳化剤、有利にはエトキシル化Ｃ_８ 〜Ｃ_２０−脂肪アルコール、殊にはＣ_９ 〜Ｃ_１６−脂肪アルコールの硫酸半エステルおよび／またはエトキシル化Ｃ_８ 〜Ｃ_３２−オキソアルコール、殊にはＣ_９ 〜Ｃ_１６−オキソアルコールの硫酸半エステルであって、平均エトキシル化度２〜５０、殊には３〜３５を有するものを含む。
【００６１】
上記の界面活性物質、殊には乳化剤は、全部または一部分を共重合体の製造の際に使用し、全部または一部分を共重合体の製造の後に加えるか、または全部または一部分を本発明による建築材料の製造のために使用の際に加えることができる。水性媒体中のラジカル乳化重合により本発明により使用される共重合体の製造の際に、乳化剤の全量の少なくとも２５質量％、有利には少なくとも３５質量％および殊に有利には少なくとも５０質量％を共重合体の製造の際に使用すると有利なことが証明されている。
【００６２】
数種の態様形では、乳化剤の全量を実質的に共重合体の製造の際に使用する。他の有利な態様形では、使用する殊にはイオン性乳化剤の全量の３０〜６５質量％、有利には３５〜６０質量％および殊に有利には４０〜５５質量％を、ラジカル乳化重合の過程で加える。乳化剤の残量は、重合終了の後に加える（後鹸化）。製造および「後鹸化」のために、同じかまたは異なる乳化剤を加えることができ、その際、複数の乳化剤の添加の場合に、乳化剤の混合比は、共重合体の製造のためと後鹸化のためとで異なることができる。殊には、後鹸化の際に、陰イオン性アルコキシル化乳化剤および／または陰イオン性非アルコキシル化乳化剤を使用できる。
【００６３】
水硬性結合剤に基づく建築材料の機械的強度の十分な改善を達成するために、通常、−６０℃以上、有利には−５０℃以上のガラス転移温度を有する共重合体の使用が推奨される。従って、共重合体は、有利にはガラス転移温度Ｔ_ｇ ＞−４５℃、殊に有利には＞−４０℃および殊には＞−３５℃を有する。
【００６４】
建築材料のたわみ性、殊には低温たわみ性の十分な改善を達成するために、水硬性結合剤に基づく建築材料中の共重合体は、フィルム化できなければならなかった。従って、本発明により使用される共重合体は、通常、＜＋４０℃、殊には＜＋３０℃、特に有利には＜＋２０℃、殊に有利には＜＋１０℃および殊には＜＋０℃のガラス転移温度Ｔ_ｇ を有する。
【００６５】
従って、本発明による使用に好適な共重合体は、約−３０℃、約−２５℃、約−２０℃、約−１５℃、約−１０℃または約−５℃のガラス転移温度Ｔ_ｇ を有する。
【００６６】
ガラス転移温度Ｔ_ｇ としては、本明細書では、ＡＳＴＭ Ｄ３４１８−８２に従って、示差熱分析（ＤＴＡ）により測定される「中間点温度」と理解する（ウルマンの「工業化学百科事典」第五版(Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A21, VCH Weinheim, 1992) １６９ページならびにゾーゼル(Zosel, Farbe und Lack 82 (1976), S. 125-134) 参照、またDIN53765も参照）。
【００６７】
異なるガラス転移温度の共重合体成分を含むポリマー分散液において、通常、少なくとも主要部分が上記の範囲内に入るガラス転移温度Ｔ_ｇ を有する場合に有利である。このような調製物は、例えば２種またはそれ以上の異なる共重合体の混合によりまたは、例えば多段重合体、核−殻構造を有するポリマー粒子またはその他の非ランダムな組成を有する共重合体粒子に導く重合方法により得られる。
【００６８】
所望の値へのガラス転移温度Ｔ_ｇ の調節は、相応するモノマーの選択によっても、また共重合体または数種の共重合体内に使用するモノマーの量比率の選択によっても行うことができる。
【００６９】
これに関連して、コポリマーＰのガラス転移温度Ｔ_ｇ を推定すると役立つことが分かっている。フォックス(T.G. Fox, Bull. Am. Phys. Soc. (Ser.II) 1、 123 (1956))およびウルマンの「工業化学百科事典」(Ullmanns Enzyklopaedie der technischen Chemie, Weinhein (1980))１７〜１８ページによると、弱く架橋した共重合体のガラス転移温度は、高い分子量において、良い近似で、
【００７０】
【数１】

【００７１】
〔式中、Ｘ^１ 、Ｘ^２ 、・・・、Ｘ^ｎ は、モノマー１、２、・・・、ｎの質量分率、およびＴ_ｇ ^１ 、Ｔ_ｇ ^２ 、・・・、Ｔ_ｇ ^ｎ は、モノマー１、２、・・・、ｎのそれぞれ一種類から構成されたポリマーの単独の絶対温度表示ガラス転移温度を表す〕が成立する。後者は、例えばウルマンの「工業化学百科事典」第Ａ２１巻(Ullmann's Encyclopedia of Industrial Chemistry, VCH Weinheim, Volume A21, 1992)１６９ページまたはブランドラップら(J. Brandrup, E.H. Immergut, Polymer Handbook 3rd. Ed. J. Wiley, New York, 1989)から知られている。
【００７２】
上記のポリマー粒径の調節の方法は、例えば欧州特許出願公開（ＥＰ−Ａ）第１２６６９９号、欧州特許出願公開（ＥＰ−Ａ）第５６７８８１号、欧州特許出願公開（ＥＰ−Ａ）第５６７８１９号、ドイツ特許出願公開（ＤＥ−Ａ）第３１４７００８号およびドイツ特許出願公開（ＤＥ−Ａ）第４２１３９６７号の各明細書から公知である。
【００７３】
有利には、本発明により使用されるポリマー分散液は、６．７〜８．０、有利には６．８〜７．５および特に有利には６．９〜７．２、例えば７．０〜７．１の範囲内のｐＨ値を有する、ポリマー分散液のｐＨ値の調節のために、有利には非揮発性塩基が使用される。好適な非揮発性塩基は、例えばカセイソーダ、カセイカリおよび例えば固体としても水溶液（水酸化カルシウム溶液）としても使用できる石灰乳が使用される。有利には、水性懸濁液としての石灰乳が使用される。特定の上記のｐＨ範囲の維持および上記の塩基の使用は、本発明により使用される分散液の使用範囲に有利に影響する。殊には、ポリマー分散液と水硬性結合剤との認容性は有利に影響する。
【００７４】
本発明により使用されるポリマー分散液は、直接、場合により固体含有量の調整の後および／または慣用の補助物質（以下に記載のようなもの）の添加の後に、水硬性結合剤に基づく建築材料に加えることができる。水性分散液を本発明に従って使用する場合には、分散液の固体含有量、すなわち非揮発性成分の割合は、通常、２０〜８０質量％の範囲内である。有利には、分散液は、固体含有量に対して、３０〜７０質量％、殊には３５〜６０質量％および殊に有利には４０〜５５質量％の水性分散液を使用する。
【００７５】
水性分散液の粘度は、５５％分散液として、ＤＩＮ５３０１９による回転粘度計を用いて２３℃、せん断速度２５０ｓ^{- １}で測定して、１０〜２５００ｍＰａｓ、有利には２０〜５００ｍＰａｓ、の範囲内にある。水性ポリマー分散液は、有機溶剤、有利には水と混合可能な有機溶剤、例えばアルコール、ジオールおよびポリオールを含むことができる。有利には、有機溶剤の含有量は、ポリマー分散液の全質量に対して１０質量％未満、殊に有利には、ポリマー分散液は実質的に有機溶剤を含まない。
【００７６】
本発明により使用されるポリマー分散液は、半エステルの形、例えばペースト状物質、または固体形、例えば粉末または顆粒としてでも使用できる。ポリマー粉末またはポリマー顆粒は、ポリマー分散液から乾燥、有利には噴霧乾燥により得られる。
【００７７】
従って、本発明の対象は、上記のポリマー分散液から揮発性成分の少なくとも８０質量％、有利には少なくとも９０質量％を除去して得られるポリマー粉末またはポリマー顆粒の、水硬性結合剤に基づく無機質建築材料への混和剤としての使用でもある。
【００７８】
ポリマー分散液、ポリマー粉末またはポリマー顆粒は、慣用の助剤を含むことができる。助剤は、通常、共重合体に対して合計して０．１〜３０質量％の量で使用する。慣用の助剤は、例えば湿潤剤、殺菌剤、殺生物剤、消泡剤、例えばＢＡＳＦ（ルードヴィヒスハーフェン(Ludwigshafen)）、ミュンチッヒ社（ハイルブロン）(Fa. Muenzig(Heilbronn))およびワッカー社（ミュンヘン）(Fa. Wacker(Muenchen))の市場で入手できる消泡剤、増粘剤、凍結防止剤、レベリング剤、柔軟剤およびフィルム形成助剤である。好適なフィルム形成助剤は、例えばエチレングリコール、プロピレングリコール、ブチレングリコール、ヘキシレングリコール、ジエチレングリコール、ジプロピレングリコール、ジブチレングリコール、これらのＣ_１ 〜Ｃ_４ −アルカノールとの半エーテル、例えばジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノフェニルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノブチルエーテル、これらのエーテル−アセタート、例えばジエチレングリコールモノエチルエーテルアセタートおよびジエチレングリコールモノブチルエーテルアセタート、プロピレングリコールモノプロピルエーテルアセタートおよびプロピレングリコールモノブチルエーテルアセタート、ジプロピレングリコール−ｎ−ブチルエーテルアセタート、さらに脂肪族モノカルボン酸およびジカルボン酸のアルキルエステル、例えばイーストマンコダック(Eastman Kodak) のテキサノール(Texanol) ^（Ｒ） またはこれらの工業的混合物、例えばＢＡＳＦ株式会社のルソルヴァン(Lusolvan)^（Ｒ） ＦＢＨ（コハク酸、グルタル酸およびアジピン酸のジ−ｎ−ブチルエステル混合物）である。柔軟剤として、すべての慣用で、分散液に適する柔軟剤、例えば（オリゴ）プロピレングリコールアルキルフェニルエーテル、例えばＢＡＳＦ株式会社のプラスチリット(Plastilit) ^（Ｒ） ３０６０が市場で入手できて、該当する。
【００７９】
本発明により使用されるポリマー分散液、ポリマー粉末またはポリマー顆粒は、追加して水硬性結合剤のための液化剤(Verfluessiger) を含むことができる。通常、水硬性結合剤のための液化剤は、水硬性結合剤に基づく建築材料の性質、殊には加工性および／または結合性の変化のための添加材である。通常、水硬性結合剤に基づく建築材料のためのこのような液化剤は、水溶性の高分子物質である。
【００８０】
本発明により使用される分散液を用いて変性された水硬性結合剤に基づく建築材料の良い加工性は、多くの場合に液化剤の存在によりさらに改善することができる。
【００８１】
有利には、ナフタレンスルホン酸−ホルムアルデヒド−縮合体、メラミン−ホルムアルデヒド−ポリ縮合体および／またはリグニンスルホナートに基づくもの、例えば欧州特許出願公開（ＥＰ−Ａ）第４０２３１９号明細書に記載のもの、ならびにカルボン酸およびジカルボン酸とスチレンとのホモポリマーおよびコポリマーに基づくもの、例えば欧州特許出願公開（ＥＰ−Ａ）第３０６４４９号明細書および米国特許（ＵＳ−Ａ）第３９５２８０５号明細書、またはイソブタンまたはジイソブタンとのもの、例えばドイツ特許出願公開（ＤＥ−Ａ）第３７１６９７４号明細書、欧州特許出願公開（ＥＰ−Ａ）第３３８２９３号明細書、ドイツ特許出願公開（ＤＥ−Ａ）第３９２５３０６号明細書、米国特許（ＵＳ−Ａ）第４５８６９６０号明細書、米国特許（ＵＳ−Ａ）第４０４２４０７号明細書および米国特許（ＵＳ−Ａ）第４９０６２９８号明細書に記載の液化剤が好適である。
【００８２】
同様に、不飽和カルボン酸と不飽和カルボン酸のヒドロキシアルキルエステルとの共重合体、例えば欧州特許（ＥＰ）第９７６１３号明細書に記載のものに基づき、共重合したカルボン酸モノマーおよびアクリル酸およびメタクリル酸のポリアルキレンオキシドエステル、例えばドイツ特許出願公開（ＤＥ−Ａ）第４４２０４４４号明細書に記載のものに基づき、エチレン性不飽和ポリオキシアルキレンエーテル、複数回不飽和アルケニルエーテルおよび無水マレイン酸、例えば欧州特許（ＥＰ）第６１９２７７号明細書に記載のものに基づき、またはマレイン酸誘導体とビニルモノマーとのコポリマー、例えばドイツ特許出願公開（ＤＥ−Ａ）第４３０４１０９号明細書および欧州特許出願公開（ＥＰ−Ａ）第６１０６９９号明細書に記載のものに基づく液化剤も好適である。
【００８３】
上記の公開文献は、ここに全体を引用する。
【００８４】
このような液化剤は、例えばＡＤＤＩＭＥＮＴ社（ハイデルベルク(Heideiberg)）、ＳＫＷ（トロストベルク(Trostberg) ）、ＢＡＳＦ（ルードヴィヒスハーフェン(Ludwigshafen)）殊にはソカラン(Sokalan) 商標、およびＤＹＣＫＥＲＨＯＦＦ（ヴィスバーデン(Wiesbaden) ）から市販され入手できる。
【００８５】
有利には、ナフタレンスルホン酸縮合体、カルボン酸モノマー共重合体、アクリル酸およびメタクリル酸のポリアルキレンオキシドエステルとに基づく液化剤を使用する。
【００８６】
本発明により使用される共重合体、すなわちポリマー分散液、ポリマー粉末またはポリマー顆粒は、水硬性結合剤に基づく建築材料に、共重合体として計算しかつ水硬性結合剤の乾燥質量に対して、有利には、５〜２５０質量％、殊に有利には１０〜１５０質量％および殊には２０〜１００質量％の量を使用する。通常、水硬性結合剤および水硬性結合剤に基づく建築材料の所望の性質改善を達成するためには、水硬性結合剤に対してポリマー１０〜５０質量％または１５〜４０質量％の混和ですでに十分である。
【００８７】
本発明により使用されるポリマー分散液、ポリマー粉末またはポリマー顆粒は、水硬性結合剤に基づく建築材料に、通常、共重合体として計算しかつ建築材料の無機質成分の乾燥質量に対して、２〜１５０質量％、有利には５〜８０質量％および殊に有利には１０〜５０質量％の量を添加する。通常、建築材料の所望の性質改善を達成するためには、水硬性結合剤に基づく建築材料の無機質成分の乾燥重量に対して、ポリマー５〜３５質量％または１０〜２５質量％の添加で十分である。
【００８８】
水硬性結合剤に基づく建築材料のための慣用の助剤は、殊には上記の助剤および液化剤である。建築材料中に使用するための好適その他の助剤は、専門家には公知であり、例えばＨ．ロイル「建築化学ハンドブック」(H. Reul, Handbuch der Bauchemie, Verlag fuer chemische Industrie, H. Ziolkowsky KG, Augsburg (1991)) に記載されている。
【００８９】
水硬性結合剤に基づく建築材料のための慣用の添加材として、例えば、無機質添加材、例えば砂利、粗砂、細砂、種々の大きさの石英砂、例えば粒径０．０８〜０．８ｍｍのもの、石英粉、例えば粒径≦０．０９ｍｍ、玄武岩、石灰石、チョーク、大理石、トラス、珪砂、沈降ケイ酸、石炭フライアッシュおよび硫酸バリウムまたは非無機質添加材、例えば有機繊維または有機多孔性物質が該当する。その他の好適な無機質または非無機質添加材は、専門家には公知であり、例えばドイツ建築化学専門現状報告書「変性無機モルタル系と環境」(Sachstandsbericht Dt. Bauchemie: Modifizierte Mineralische Moertalsysteme and Umwelt (1. Ausgabe, Juli 1998) ）に記載されている。
【００９０】
同様に本発明の対象は、上記のポリマー分散液、これから得られるポリマー粉末またはポリマー顆粒を、いずれも共重合体として計算し、無機成分の乾燥質量に対して、２〜１５０質量％、有利には５〜８０質量％および殊に有利には５〜３０質量％含む水硬性結合剤に基づく建築材料を含む。
【００９１】
本発明による使用によりその性質を改善できる水硬性結合剤に基づく代表的な建築材料は、セメント、液体セメント、コンクリート、モルタル、しっくい、たたき、結合剤調製物、殊にはセメントに基づくもの、路面舗装およびタイル接着剤である。有利な建築材料は、殊には無機質シール剤である。
【００９２】
建築材料は、その使用目的および加工段階に応じて、固体形（例えば調合水ならびにポリマー分散液の添加の前または硬化の後）、液体状ならびに粘度の高い液状または多孔性形で存在することができる。
【００９３】
当然ながら、ポリマー分散液から得られたポリマー粉末は、建築資材内に使用する前に無機質結合剤と混合できる。このような調製物は、水硬性結合剤、有利にはセメント、およびポリマーを通常主要成分として含む。さらに、これらの調製物は、慣用の無機質または非無機質添加材および慣用の助剤、例えば上記のものを含むことができる。
【００９４】
さらに、本発明は、水硬性結合剤およびポリマー分散液、ポリマー粉末またはポリマー顆粒および場合により水および／または添加材を一緒に混合した、水硬性結合剤に基づく建築材料の機械的強度、弾性および加工性を改善するための方法に関する。好適な混合技術および混合装置は、専門家には公知であり、例えばウルマン「工業化学百科事典」第三版、１９５１、第１巻、６９３〜７２７ページに記載されている。
【００９５】
ポリマー分散液、ポリマー粉末またはポリマー顆粒の本発明による使用は、従来技術の水硬性結合剤に基づくポリマー変性建築材料と比較して、ポリマーと水硬性結合剤との混合の際およびその後でも、不快な臭気を全くまたはごく僅か発生するに過ぎないことを特徴とするポリマー変性懸濁液散る材料をもたらす。ポリマー分散液、ポリマー粉末またはポリマー顆粒の本発明による使用は、さらに、無機質結合剤に基づく多数の建築材料において、固化または結合した状態で改善された性質に、殊には高い機械的強度、例えば高いたわみ性、高い破断強度および／または高い凝集力をもたらす。固化または結合した状態の建築材料の耐水性が改善され、またその吸水性は著しく低下する。通常、固化前の水硬性結合剤に基づく建築材料の加工性も、例えば有利ないわゆる「可使時間」によりおよび液状、半固体状またはペースト状建築材料への水硬性結合剤の混合またはスラリー化の際の型への低い接着または粘着により改善される。殊に有利には、本発明による分散液、ポリマー粉末または顆粒の性質は、セメントに基づく建築材料に利用される。
【００９６】
本発明によるポリマー分散液は、当然ながら非セメント系の利用、殊には充填材を含む被覆系、特にはたわみ性被覆系例えばたわみ性屋根被覆材料およびシール材ならびに接着材、特には充填剤を含む建築用接着材例えばタイル接着剤に好適である。
【００９７】
たわみ性屋根被覆材料の代表的な配合は、水の他に本発明によるポリマー分散液を含む。顔料、例えば二酸化チタンまたは硫酸バリウムおよび充填材例えば炭酸カルシウム、チョーク、タルク、粘土ならびに慣用の助剤、例えば殺生物剤、湿潤剤、フィルム形成助剤、例えば炭化水素例えばガソリン、柔軟剤、溶剤および凍結防止剤、例えばグリセリンまたはグリコール、増粘剤（例えば会合性増粘剤）および消泡剤。顔料の割合は、通常、共重合体１重量部に対して１〜５重量部の範囲内にある。助剤の割合は、通常、共重合体１００重量部に対して０．５〜２５重量部の範囲内にある。
【００９８】
たわみ性屋根被覆材料被覆材の代表的な組成は、ここに引用する欧州特許出願公開（ＥＰ−Ａ）第５０１２７２号の実施例２に記載され、その際、これに記載のポリマー分散液を本発明によるポリマー分散液に置き換える。たわみ性屋根被覆材料被覆材の別の配合は、Ｌ．チャンダー(L. Chander, Paint & Resin 9/10, 1981, 24-25ページ) に記載され、その際、これに使用されたポリマー分散液を同様に本発明による共重合体の分散液に置き換えることができる。
【００９９】
タイル接着剤の代表的な配合は、本発明による共重合体および水の他に、また充填材、例えば上記の充填材および／またはケイ酸塩、またはケイ酸、さらには補助材、例えば上記の補助材を含む。充填材の割合は、通常、共重合体１質量部に対して５〜１０質量部である。補助材の割合は、通常、共重合体１００質量部に対して１〜２０質量部である。タイル接着剤の代表的な配合は、ここに引用する欧州特許出願公開（ＥＰ−Ａ）第３５３２２号の実施例２および４に記載されている。ここに記載の重合体分散液は、本発明による共重合体−分散液と交換できる。
【０１００】
下記の実施例で本発明を制限することなく説明する。
【０１０１】
【実施例】
本発明の実施例に使用する本発明によるポリマー分散液および比較例のポリマー分散液は、水性媒体中のラジカル重合により得られた。
【０１０２】
ポリマー分散液の共重合体内に一緒に重合されたモノマーの質量％で表した一覧を第１表に記載する。ポリマー分散液の固体含有量（すなわち非揮発性部分）は、空気循環式乾燥器内、１２０℃で２時間乾燥による試料の質量損失（約１ｇ）から測定した。ポリマー分散液の粘度は、パール・フィジカ社(Firma Paar Physica)の回転粘度計（レオマート(Rheomat) ）を用いて、ＤＩＮ５３０１９に従って、２３℃においてせん断速度２５０-1で測定した。ガラス転移温度Ｔ_ｇ は、メットラー・トレド社(Fa. Mettler Toledo)の示差熱量計ＤＳＣ８２０を用い、５℃／分の直線加熱速度で測定した。
【０１０３】
Ｉ．本発明によるポリマー分散液の製造
分散液ＥＤ１
アンカー型攪拌機（１２０回転／分）を有する２ｌガラス容器内に、完全脱塩水２００ｇを装入した。内部温度８５℃において、供給物(Zulauf)１の全量の５質量％および供給物２の全量の１０質量％を加えた。装入物を１０分間、８５℃で重合開始させた。引き続いて８５℃において、３．５時間内に供給物１および供給物２の残量を空間的に別々に連続して加えた。さらに３０分間この温度に置いた後冷却し、次いで反応混合物を２０質量％水酸化カルシウム水溶液を用いて中和した。攪拌しながら供給物３を加えた。このようにして製造した調製物は、非揮発性成分４９．８質量％を含み、かつｐＨ値７．２を有していた。粘度は６７ｍＰａｓであった。分散液内に含まれた共重合体は、−１４℃のガラス転移温度Ｔ_ｇ を有していた。
【０１０４】
供給物１：
完全脱塩水 １８５ｇ
エトキシル化度約３０を有するエトキシル化ラウリルアルコールの硫酸半エステ
ルのナトリウム塩の３０質量％水溶液（ヘンケル社(Fa. Henkel)のディスポニル
(Disponil)ＦＥＳ７７）；以下では乳化剤溶液Ｉ １７ｇ
エトキシル化度約１８を有するエトキシル化Ｃ_１６／Ｃ_１８−アルコールの２０
質量％水溶液；以下では乳化剤溶液ＩＩ １３ｇ
スチレン １１０ｇ
ｎ−ブチルアクリレート ３８５ｇ
アクリロニトリル １７ｇ
２−ヒドロキシエチルアクリレート ３３ｇ
メタクリル酸 ６ｇ
供給物２：
完全脱塩水 ６０ｇ
ペルオキソ二硫酸ナトリウム ２ｇ
供給物３：
乳化剤溶液Ｉ ８ｇ
乳化剤溶液ＩＩ ２５ｇ
分散液ＥＤ２
アンカー型攪拌機（１２０回転／分）を有する２ｌガラス容器内に、完全脱塩水３２０ｇを装入した。内部温度８５℃において、供給物１の全量の５質量％および供給物２の全量の１０質量％を加えた。装入物を１０分間、８５℃で重合開始させた。引き続いて８５℃において、３．５時間内に供給物１および供給物２の残量を空間的に別々に連続して加えた。さらに３０分間この温度に置いた後冷却し、次いで反応混合物を２０質量％水酸化カルシウム水溶液を用いて中和した。攪拌しながら供給物３を加えた。このようにして製造した分散液は、非揮発性成分４９．２質量％を含み、かつｐＨ値７．０を有していた。粘度は４６ｍＰａｓであった。分散液内に含まれた共重合体は、−２０℃のガラス転移温度Ｔ_ｇ を有していた。
【０１０５】
供給物１：
完全脱塩水 ３７１ｇ
乳化剤溶液Ｉ ３０ｇ
乳化剤溶液ＩＩ ２３ｇ
スチレン １８０ｇ
ｎ−ブチルアクリレート ７２５ｇ
２−ヒドロキシエチルアクリレート ９０ｇ
メタクリル酸 ５ｇ
供給物２：
完全脱塩水 １２０ｇ
ペルオキソ二硫酸ナトリウム ４ｇ
供給物３：
乳化剤溶液Ｉ １４ｇ
乳化剤溶液ＩＩ ４５ｇ
分散液ＥＤ３
アンカー型攪拌機（１２０回転／分）を有する４ｌガラス容器内に、完全脱塩水４５０ｇを装入した。内部温度８５℃において、供給物１の全量の５質量％および供給物２の全量の１０質量％を加えた。装入物を１０分間、９０℃で重合開始させた。引き続いて９０℃において、３時間内に供給物１および３．５時間内に供給物２の残量を空間的に別々に加えた。さらに３０分間この温度に置いた後反応混合物を冷却し、次いで２０質量％水酸化カルシウム水溶液を用いて中和した。このようにして製造したポリマー分散液は、非揮発性成分５４．９質量％を含み、かつｐＨ値７．０を有していた。粘度は１４８ｍＰａｓであった。含まれた共重合体は、−８℃のガラス転移温度Ｔ_ｇ を有していた。
【０１０６】
供給物１：
完全脱塩水 ５３９ｇ
エトキシル化度約２５を有するエトキシル化ノニルフェノールの硫酸半エステル
のナトリウム塩の２５質量％水溶液、以下では乳化剤溶液ＩＩＩ ２８ｇ
エトキシル化度約２５を有するエトキシル化オクチルフェノールの硫酸半エステ
ルのナトリウム塩の２０質量％水溶液；以下では乳化剤溶液ＩＶ ２０ｇ
ｎ−ブチルアクリレート ９６０ｇ
メチルメタクリレート ３９０ｇ
２−ヒドロキシエチルアクリレート １３５ｇ
アクリル酸 １５ｇ
供給物２：
完全脱塩水 ９５ｇ
ペルオキソ二硫酸ナトリウム ７ｇ
分散液ＥＤ４
アンカー型攪拌機（１２０回転／分）を有する４ｌガラス容器内に、完全脱塩水４５０ｇを装入した。内部温度８５℃において、供給物１の全量の５質量％および供給物２の全量の１０質量％を加えた。装入物を１０分間、８５℃で重合開始させた。引き続いて８５℃において、３．５時間内に供給物１および供給物２の残量を空間的に別々に加えた。さらに３０分間この温度に置いた後反応混合物を冷却し、次いで２０質量％水酸化カルシウム水溶液を用いて中和した。攪拌しながら供給物３を加えた。このようにして製造したポリマー分散液は、非揮発性成分５０．４質量％を含み、かつｐＨ値７．０を有していた。粘度は４５ｍＰａｓであった。含まれた共重合体は、−３１℃のガラス転移温度Ｔ_ｇ を有していた。
【０１０７】
供給物１：
完全脱塩水 ４１３ｇ
乳化剤溶液Ｉ ３５ｇ
乳化剤溶液ＩＩ ２６ｇ
２−エチルヘキシルアクリレート ４２０ｇ
ｎ−ブチルアクリレート ４２０ｇ
スチレン ２１０ｇ
２−ヒドロキシエチルアクリレート ６３ｇ
供給物２：
完全脱塩水 ９０ｇ
ペルオキソ二硫酸ナトリウム ４ｇ
供給物３：
乳化剤溶液Ｉ １８ｇ
乳化剤溶液ＩＩ ５３ｇ
分散液ＥＤ５
アンカー型攪拌機（１２０回転／分）を有する４ｌガラス容器内に、完全脱塩水４５０ｇを装入した。内部温度８５℃において、供給物１の全量の５質量％および供給物２の全量の１０質量％を加えた。装入物を１０分間、８５℃で重合開始させた。引き続いて８５℃において、３．５時間内に供給物１および供給物２の残量を空間的に別々に加えた。さらに３０分間この温度に置いた後反応混合物を冷却し、次いで２０質量％水酸化カルシウム水溶液を用いて中和した。攪拌しながら供給物３を加えた。このようにして製造したポリマー分散液は、非揮発性成分５０．３質量％を含み、かつｐＨ値６．９を有していた。粘度は４４ｍＰａｓであった。含まれた共重合体は、−２６℃のガラス転移温度Ｔ_ｇ を有していた。
【０１０８】
供給物１：
完全脱塩水 ４１３ｇ
乳化剤溶液Ｉ ３５ｇ
乳化剤溶液ＩＩ ２６ｇ
２−エチルヘキシルアクリレート ３６８ｇ
ｎ−ブチルアクリレート ４２０ｇ
スチレン ２６３ｇ
２−ヒドロキシエチルアクリレート ６３ｇ
供給物２：
完全脱塩水 ９０ｇ
ペルオキソ二硫酸ナトリウム ４ｇ
供給物３：
乳化剤溶液Ｉ １８ｇ
乳化剤溶液ＩＩ ５３ｇ
分散液ＥＤ６
アンカー型攪拌機（１２０回転／分）を有する２ｌガラス容器内に、完全脱塩水２５０ｇを装入した。内部温度８５℃において、供給物１の全量の５質量％および供給物２の全量の１０質量％を加えた。装入物を１０分間、８５℃で重合開始させた。引き続いて８５℃において、３．５時間内に供給物１および供給物２の残量を空間的に別々に加えた。さらに３０分間この温度に置いた後反応混合物を冷却し、次いで２０質量％水酸化カルシウム水溶液を用いて中和した。攪拌しながら供給物３を加えた。このようにして製造したポリマー分散液は、非揮発性成分５０．３質量％を含み、かつｐＨ値７．０を有していた。粘度は４７ｍＰａｓであった。含まれた共重合体は、−２５℃のガラス転移温度Ｔ_ｇ を有していた。
【０１０９】
供給物１：
完全脱塩水 ２５０ｇ
乳化剤溶液Ｉ １８ｇ
乳化剤溶液ＩＩ １４ｇ
２−エチルヘキシルアクリレート ２２０ｇ
ｎ−ブチルアクリレート １９３ｇ
スチレン １３８ｇ
２−ヒドロキシエチルアクリレート ２２ｇ
供給物２：
完全脱塩水 ５０ｇ
ペルオキソ二硫酸ナトリウム ２ｇ
供給物３：
乳化剤溶液Ｉ ９ｇ
乳化剤溶液ＩＩ ２８ｇ
ＩＩ．比較分散液の製造
比較分散液ＶＤ１
アンカー型攪拌機（１２０回転／分）を有する２ｌガラス容器内に、完全脱塩水２８０ｇを装入した。内部温度８５℃において、供給物１の全量の５質量％および供給物２の全量の１０質量％を加えた。装入物を１０分間、８５℃で重合開始させた。引き続いて８５℃において、３．５時間内に供給物１および供給物２の残量を空間的に別々に加えた。さらに３０分間この温度に置いた後反応混合物を冷却し、次いで２０質量％水酸化カルシウム水溶液を用いて中和した。攪拌しながら供給物３を加えた。このようにして製造したポリマー分散液は、非揮発性成分５０．３質量％を含み、かつｐＨ値７．２を有していた。粘度は４８ｍＰａｓであった。含まれた共重合体は、−２４℃のガラス転移温度Ｔ_ｇ を有していた。
【０１１０】
供給物１として下記を使用した：
完全脱塩水 １１６ｇ
乳化剤溶液Ｉ １５ｇ
乳化剤溶液ＩＩ ２３ｇ
２−エチルヘキシルアクリレート ２８８ｇ
スチレン ７２ｇ
アクリロニトリル ７４ｇ
２−ヒドロキシエチルアクリレート ３８ｇ
メタクリル酸 ７ｇ
供給物２として下記を使用した：
完全脱塩水 １００ｇ
ペルオキソ二硫酸ナトリウム ３ｇ
供給物３として下記を使用した：
乳化剤溶液Ｉ ８ｇ
乳化剤溶液ＩＩ １５ｇ
比較分散液ＶＤ２
アンカー型攪拌機（１２０回転／分）を有する２ｌガラス容器内に、完全脱塩水１７０ｇを装入した。内部温度８５℃において、供給物１の全量の５質量％および供給物２の全量の１０質量％を加えた。装入物を１０分間、８５℃で重合開始させた。引き続いて８５℃において、３．５時間内に供給物１および供給物２の残量を空間的に別々に加えた。さらに３０分間この温度に置いた後反応混合物を冷却し、次いで２０質量％水酸化カルシウム水溶液を用いて中和した。攪拌しながら供給物３を加えた。このようにして製造したポリマー分散液は、非揮発性成分４８．９質量％を含み、かつｐＨ値７．０を有していた。粘度は３８８ｍＰａｓであった。含まれた共重合体は、−２１℃のガラス転移温度Ｔ_ｇ を有していた。
【０１１１】
供給物１として下記を使用した：
完全脱塩水 １９７ｇ
乳化剤溶液Ｉ １５ｇ
乳化剤溶液ＩＩ １１ｇ
２−エチルヘキシルアクリレート ３９１ｇ
スチレン １７６ｇ
アクリロニトリル １６ｇ
アクリルアミド ３８ｇ
メタクリル酸 ９ｇ
供給物２として下記を使用した：
完全脱塩水 ６０ｇ
ペルオキソ二硫酸ナトリウム ２ｇ
供給物３として下記を使用した：
乳化剤溶液Ｉ ８ｇ
乳化剤溶液ＩＩ ２３ｇ
比較分散液ＶＤ３
アンカー型攪拌機（１２０回転／分）を有する４ｌガラス容器内に、完全脱塩水５００ｇを装入した。内部温度８５℃において、供給物１の全量の５質量％および供給物２の全量の１０質量％を加えた。装入物を１０分間、８５℃で重合開始させた。引き続いて８５℃において、３．５時間内に供給物１および供給物２の残量を空間的に別々に加えた。さらに３０分間この温度に置いた後反応混合物を冷却し、次いで２０質量％水酸化カルシウム水溶液を用いて中和した。攪拌しながら供給物３を加えた。このようにして製造したポリマー分散液は、非揮発性成分４９．４質量％を含み、かつｐＨ値７．２を有していた。粘度は２９８ｍＰａｓであった。含まれた共重合体は、−２０℃のガラス転移温度Ｔ_ｇ を有していた。
【０１１２】
供給物１として下記を使用した：
完全脱塩水 ５６１ｇ
乳化剤溶液Ｉ ４３ｇ
乳化剤溶液ＩＩ ３３ｇ
２−エチルヘキシルアクリレート ８５３ｇ
スチレン ３８２ｇ
アクリロニトリル ２９ｇ
２−ヒドロキシエチルアクリレート １１８ｇ
メタクリル酸 ８８ｇ
供給物２として下記を使用した：
完全脱塩水 １２０ｇ
ペルオキソ二硫酸ナトリウム ５ｇ
供給物３として下記を使用した：
乳化剤溶液Ｉ ２２ｇ
乳化剤溶液ＩＩ ６５ｇ
比較分散液ＶＤ４
この分散液の製造は、分散液ＶＤ３の製造と同様にして行った。
【０１１３】
供給物１として下記を使用した：
完全脱塩水 ３９９ｇ
ドデシル硫酸ナトリウムの１５質量％水溶液（乳化剤溶液Ｖ） １４０ｇ
２−エチルヘキシルアクリレート ９２８ｇ
スチレン ４３３ｇ
アクリロニトリル ３９ｇ
２−ヒドロキシエチルアクリレート １２４ｇ
メタクリル酸 ２３ｇ
供給物２として下記を使用した：
完全脱塩水 １２０ｇ
ペルオキソ二硫酸ナトリウム ５ｇ
供給物３として下記を使用した：
乳化剤溶液Ｖ １４０ｇ
このようにして製造したポリマー分散液は非揮発性成分５０．０質量％を含み、かつｐＨ値６．９を有していた。粘度は７６ｍＰａｓであった。含まれた共重合体は、−２１℃のガラス転移温度Ｔ_ｇ を有していた。
【０１１４】
ＩＩＩ．安定性の試験
分散液の安定性の基準として、凝集物形成、せん断安定性および電解質安定性を下記のようにして測定した。
【０１１５】
乳化重合の際の凝集体形成の傾向は、冷却および中和したポリマー分散液を網目４５μｍのペルロンふるい(Perlonsieb)を通して濾過して測定した。記載した凝縮値は、ポリマー分散液の全質量に対する表面乾燥した後の濾過残留物の割合を表す。
【０１１６】
せん断安定性の試験のために、それぞれの分散液について、ディスペルマート(Dispermat) （ＶＭＡゲッツマン有限会社(VMA Getzmann GmbH) ）を用いて非希釈試料を１０分間、１００００回転／分でせん断負荷した。引き続いて、少量の試料をガラス支持体上に塗布した。比較のために、少量の未せん断負荷分散液も同様にガラス支持体上に塗布し、次いで凝集物ならびに微細凝集物（いわゆる「ストリップ(Strippen)」の含有量を比較して試験した。未せん断負荷試料と比較して凝集物含有量ならびにストリップ含有量の著しい上昇の場合には、試料はせん断安定性でないとした。
【０１１７】
電解質安定性の試験のために、それぞれの分散液の試料を、２３℃でテンパリングし次いで一定濃度の攪拌している塩化カルシウム水溶液に滴下して加えた（塩化カルシウム含有量０．５〜７．５質量％の塩化カルシウム溶液それぞれ５０ｇ）。第１表には、それぞれの分散液について、それぞれの分散液の試料がまだ安定であった溶液の塩化カルシウム濃度を記載してある。
【０１１８】
結果を表２に纏めた。
【０１１９】
ＩＶ．応用技術的性質の試験
ポリマー分散液の親水性の尺度として、それぞれのポリマー分散液からのフィルムの吸水率を試験した。循環式乾燥器内で７日間、５０℃で乾燥して、それぞれのポリマー分散液から乾燥層厚さ約７５０μｍのポリマーフィルムを製造した。フィルムから、いずれも長さ２ｃｍおよび幅１ｃｍの試験片を切り取り、次いで２４時間、室温で水中に貯蔵した。引き続いて、試験片を表面的に乾燥し、秤量した。吸水率は、水中貯蔵の後と前のフィルム質量の比から算出した。
【０１２０】
水硬性結合剤に基づく建築材料への混和剤としての応用性質の測定のために、ポリマー分散液で変性したセメント系材料を製造した。このために、ポルトランドセメントＰＺ ４５Ｆ（ＣＥＭ Ｉ ４２．５ Ｒ）１８２質量部、それぞれのポリマー分散液（固体含有量５０質量％に調整）２１８質量部、水５３質量部、石英粉（粒径≦０．０９ｍｍ）１４９質量部、石英砂（粒径０．０８〜０．２ｍｍ）１６４質量部、石英砂（粒径０．２〜０．５ｍｍ）２１８質量部、ＢＡＳＦ株式会社の消泡剤ルミテン(Lumiten) ^（Ｒ） Ｅ−Ｐ３１０８ １４質量部およびミュンチッヒ社の消泡剤アギタン(Agitan)^（Ｒ） ２８１ ２質量部を一緒に加え混合した。
【０１２１】
すべての成分の添加および混合の後、いわゆる「可使時間」、すなわち、セメント系材料が割れないかまたは材料内の固体粒子がまだ塑性で成形できる時間を測定した。使用のために有利には、３０分を越える可使時間である。
【０１２２】
臭気発生傾向を測定するために、それぞれのポリマー変性セメント系材料の製造直後に試料を採取し、次いで閉鎖容器内で３０分間、５０℃で乾燥器内で加温した。引き続いて、臭気試験を行い、また湿潤ｐＨ紙を用いて容器内の気体空間内でアンモニアの形成を試験した。
【０１２３】
得られたセメント系材料の強度および弾性を試験するために、これらから湿潤層厚さ２ｍｍのセメントフィルムを作製した。フィルムを２８日間標準条件（２３℃、相対湿度５０％）下で硬化した。引き続いて、ＤＩＮ５３４５５に従って、フィルムの引張力および破断伸びを、自動材料試験装置を用いて引張速度１００ｍｍ／分で測定した。応用技術的試験の結果を表２に纏めた。
【０１２４】
第１表において、分散液内に含まれた共重合体のモノマー組成は質量％で統一した。ここで、ｎＢＡはｎ−ブチルアクリレート、Ｓはスチレン、ＡＮはアクリロニトリル、ＨＥＡは２−ヒドロキシエチルアクリレート、ＭＡＳはメタクリル酸、ＥＨＡは２−エチルヘキシルアクリレート、ＭＭＡはメチルメタクリレート、ＡＳはアクリル酸、ＭＡＮはメタクリロニトリルおよびＡＭはアクリルアミドを表す。
【０１２５】
固体として算出し、共重合体に対する乳化剤含有量は、ＥＤ３の除くすべての分散液において約３質量％であった。分散液ＥＤ３の乳化剤含有量は約１．１質量％であった。
【０１２６】
【表１】

【０１２７】
【表２】

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to the use of ammonia-free polymer dispersions and polymer powders or polymer granules obtained from polymer dispersions as admixtures for inorganic building materials based on hydraulic binders.
[0002]
[Prior art]
Hydraulic binders are processed into plastic materials in the wet state, together with water and optionally admixtures and conventional auxiliaries, which can be left in air or applied in water, sometimes at elevated temperatures. Thus, it is understood as an inorganic substance that hardens like a stone after a certain time. Examples of hydraulic binders are cement, gypsum, lime and clay.
[0003]
The use of polymer dispersions or polymer powders or polymer granules obtained therefrom for improving the properties of building materials based on hydraulic binders is known in principle. Polymer dispersions for use with hydraulic binders usually have a high proportion of polar and / or ionic auxiliary monomers such as (meth) acrylic acid and (meth) acrylamide and a high content of emulsifiers . These measures must increase the stability of the dispersion in the presence of the hydraulic binder, because the high electrolyte content of the hydraulic binder leads to significant destabilization of the dispersion. Because.
[0004]
Due to the increased mechanical strength of building materials based on hydraulic binder in the cured state, the polymer has a high glass transition temperature (T_g Polymer dispersions with) are often used. That is, European Patent Application Publication (EP-A) 537411 describes T_g Describes the use of polymer dispersions having> + 30 ° C. as admixtures. This admixture improves the strength of the cement-binding material and extends the pot life.
[0005]
JP 59-146963 likewise describes polymer dispersions having a high glass transition temperature for this field of application. These are only "hard monomers" such as styrene, methyl methacrylate, acrylonitrile or vinyl chloride over 90% and hydrophilic comonomers such as acrylamide, sodium styrene sulfonate, hydroxyethyl methyl acrylate or sodium vinyl sulfonate 0.02-10% including. The use of these dispersions as cement admixtures leads to cement-based building materials with high water resistance as well as partially improved compressive strength.
[0006]
Building materials based on hydraulic binders containing such polymer dispersions are relatively brittle and in particular exhibit low low temperature flexibility. This is a high polymer T_g For this reason, it is assumed that the film formation of latex particles in the building material does not occur.
[0007]
Therefore, to reduce the brittleness of cured building materials based on hydraulic binders and to increase low temperature flexibility, a low T_g A polymer dispersion containing a polymer having is used. That is, Austrian Patent (AT) 359904 describes a T of −70 to −8 ° C. as an admixture for cement-containing building materials._g Describes the use of polymer dispersions having This means that by mixing 3 to 35% by mass of the dispersion, a mortar having high low temperature flexibility after curing can be obtained. However, the incorporation of this dispersion leads to building materials with low strength.
[0008]
JP-A-63-55143 and JP-A-64-5935 disclose acrylic acid-C₄ ~ C₈ -Alkyl esters of 55-90% by weight, acrylonitrile and / or styrene 5-40% by weight, acrylic acid and / or methacrylic acid 1-10% by weight and at least one 2-hydroxyethyl- or 2-hydroxypropyl- A polymer dispersion comprising a polymer consisting of 1 to 10% by weight of (meth) acrylate and / or (meth) acrylamide and produced by emulsion polymerization in the presence of a nonionic emulsifier is described. The use of these polymer dispersions leads to building materials that have high flexibility and a low tendency to crack formation. However, more than 40% by weight of the polymer dispersion must be added. The building materials obtained thereby exhibit unsatisfactory high water absorption and often have an unpleasant odor. This is presumed to be caused by gaseous ammonia produced by partial hydrolysis of the polymer.
[0009]
JP-A-63-156048 is obtained by polymerizing together 2 to 10% by weight of an unsaturated monomer having a hydroxyl group and 30 to 98% by weight of an alkyl acrylate ester having no hydroxyl group. The use of polymer dispersions substantially free of unsaturated carboxylic acids and carboxylic acid amides is recommended. Use of this dispersion in cement-containing materials results in good adhesion capacity and high creep resistance. However, the hydrolysis resistance of this polymer dispersion and thus its stability in cement-containing materials is insufficient. Furthermore, the incorporation of the dispersion leads to an unpleasant odor of the polymer-modified cement-containing material, which is presumed to be due to the liberation of the ammonia used during neutralization of the dispersion.
[0010]
[Problems to be solved by the invention]
Accordingly, the present invention provides an aqueous polymer that has high shear strength and hydrolysis resistance, and that when mixed with a building material based on a hydraulic binder, provides improved mechanical properties to the building material in a cured state. Based on the challenge of providing a dispersion. In particular, the dispersion must lead to a building material having good processability and at the same time high flexibility, especially at low temperatures, and strength. The polymer must have a safe odor in the presence of a hydraulic binder.
[0011]
[Means for Solving the Problems]
This challenge is as a monomer
a) Acrylic acid and C₂ ~ C₁₂-40-80% by weight of at least one ester with an alkanol,
b) at least one vinyl aromatic monomer and / or methacrylic acid and C₁~ C₄ -10-40% by weight of at least one ester with alkanol,
c) C₂ ~ C₁₀-2 to 15% by weight of at least one monoester of alkanediol and acrylic acid or methacrylic acid,
d) at most 1.0% by weight of ethylenically unsaturated monomers having at least one acid group, or salts thereof;
e) less than 5% by weight of ethylenically unsaturated nitrile and
f) α, β ethylenically unsaturated monocarboxylic acid and dicarboxylic acid amide less than 1% by weight
This is solved by an aqueous, ammonia-free polymer dispersion comprising at least one copolymer which is polymerized together.
[0012]
The invention is therefore based on the use of the aqueous polymer dispersion defined above as an admixture for building materials based on hydraulic binders. At that time, the copolymer contained in the polymer dispersion according to the present invention acts as a film-forming component. The building materials based on hydraulic binders in the sense of the present invention are hydraulic binders themselves, as well as at least 5% by weight, in particular 10% by weight and very particularly preferably at least 25% by weight. It is also a building material and a building material containing at least one hydraulic binder with respect to the total mass of the agent and additive. Preference is given to the use in building materials containing cement as a binder.
[0013]
Building materials based on hydraulic binders are generally converted into forms that can be processed, mostly liquid or plastically deformable materials, with the addition of water (formulated water) and optionally conventional mineral and / or non-mineral additives. Is done. Even if these materials are usually left to stand, they cure over time. Typical building materials based on hydraulic binders that can be processed in this way are cement, mortar, plaster, tile adhesives, mineral seals, concrete and the like. These building materials are substantially distinguished by the amount and type of additive and / or moisture contained in the building.
[0014]
According to the invention, the polymer dispersion described herein is added to building materials based on hydraulic binders. The blending can be done, for example, by conversion of the building material to a workable form, for example, by replacement of at least a portion of the formulated water with the polymer dispersion described herein. The use according to the invention of polymer dispersions is also possible in the form of powders or granules obtained by drying the dispersion. These powders or granules can be added to building materials based on hydraulic binders either in the dry state (ie before water addition) and during or after water addition.
[0015]
All statements regarding the amount of building materials based on hydraulic binders and hydraulic binders are relative to their solid content, unless stated otherwise. The solid content of building materials based on hydraulic binders and hydraulic binders can be measured by drying at 120 ° C. for 24 hours. It is understood that the inorganic part is the total amount of dry solids of the building material, i.e. hydraulic binders and additives, which are free of organic and porous materials. In many cases, the mineral part of building materials based on hydraulic binders can be measured by calcination of optionally ground building material samples.
[0016]
All descriptions of amounts relating to the polymer dispersions used according to the invention and their components, in particular copolymers, emulsifiers and optional auxiliary substances, are calculated as solids unless stated otherwise. The solids content of the polymer dispersion and liquid dispersion components, eg, most solutions of emulsifiers, can be measured by drying to a constant weight at 120 ° C.
[0017]
Preferably, the copolymer dispersed in water as polymer particles is present as polymer particles having an average particle size in the range of 50 to 1000 nm, in particular 50 to 500 nm, particularly preferably 60 to 300 nm. . The copolymer contains ethylenically unsaturated monomers polymerized together. The description of the amount of monomers polymerized together is 100% by mass in total. The average particle size is adjusted by a known method, for example, by introducing seed latex, by seed latex formed at the start of polymerization in situ, by emulsifier concentration, or by a combination of these means.
[0018]
Advantageously, the copolymer comprises acrylic acid and C as monomers.₂ ~ C₁₂At least one ester with alkanol, 55 to 80% by weight and particularly preferably 60 to 75% by weight, polymerized together. Preferred C₂ ~ C₁₂The alkanol is linear C₂ ~ C₁₂-Alkanol, branched C₃ ~ C₁₂Alkanol and C₅ ~ C₁₀-Cycloalkanol. Particularly preferably, linear or branched C₂ ~ C₈ -An alkanol. Examples of monomers a) are ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 3-methylbutyl acrylate, 2-methylbutyl acrylate, n -Pentyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, 2-propylheptyl acrylate, iso-bornyl acrylate, norbornyl acrylate, 4-t-butylcyclohexyl Acrylates and 2,3,5-trimethylcyclohexyl acrylate. Particular preference is given to ethyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate, and mixtures thereof.
[0019]
Advantageously, the copolymer is used as monomer b) at least one single unsaturated vinyl aromatic monomer and / or C₁ ~ C₄ 12 to 35% by weight, and particularly preferably 15 to 30% by weight, of at least one methacrylic acid ester of alkanol. Suitable vinyl aromatics are styrene, α-methylstyrene, α-phenylstyrene, o-chlorostyrene, vinyl toluene and mixtures thereof. A particularly preferred vinyl aromatic is styrene. Preferred C₁ ~ C₄ Methacrylic esters of alkanols are, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate and t-butyl methacrylate, preferably methyl methacrylate It is. A particularly preferred monomer b) is styrene.
[0020]
Monomers a) and b) (main monomers) are generally in total 80 to 98%, preferably 85 to 98% and particularly preferably 90 to 97% by weight of all monomers polymerized together. %. Particularly preferred monomer combinations consisting of monomer b) and monomer a) are styrene / n-butyl acrylate, styrene / n-butyl acrylate / 2-ethylhexyl acrylate, styrene / 2-ethylhexyl acrylate, methyl methacrylate / n-butyl. Acrylate, methyl methacrylate / n-butyl acrylate / 2-ethylhexyl methacrylate, methyl methacrylate / 2-ethylhexyl acrylate, styrene / methyl methacrylate / n-butyl acrylate, styrene / methyl methacrylate / n-butyl acrylate / 2-ethylhexyl acrylate is there.
[0021]
Advantageously for use in the present invention, for example
A copolymer comprising at least one acrylate selected from styrene and n-butyl acrylate, 2-ethylhexyl acrylate and ethyl acrylate as the main monomer, or
A copolymer comprising at least one acrylate selected from methyl methacrylate and n-butyl acrylate and 2-ethylhexyl acrylate as main monomers
It is.
[0022]
Advantageously, the copolymer is C as monomer c).₂ ~ C₁₀-3-12% by weight and particularly preferably 3-9% by weight of at least one monoester of alkanediol and acrylic acid or methacrylic acid are polymerized together. Suitable alkanediols are linear C₂ ~ C₁₀-Alkanediol, branched C₃ ~ C₁₀-Alkanediol and C₅ ~ C₁₀A cycloalkanediol, preferably linear C₂ ~ C₆ -Α, ω-alkanediol. Examples of suitable monomers c) are hydroxyethyl acrylate, hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate and 4-hydroxy Butyl methacrylate.
[0023]
According to the invention, the copolymer is polymerized together with at most 1.0% by weight of an ethylenically unsaturated monomer or salt thereof having at least one acid group, for example a carboxyl group or a sulfonic acid group, as monomer d). Included. Thus, the copolymer is preferably at least one monomer d) 0.1 to 1.0% by weight, in particular 0.2 to 1% by weight, in particular 0.2 to 0.8% by weight. Which are polymerized together or which are substantially free of monomers d) which polymerize together (weight percentage <0.1, in particular <0.05 and particularly preferably 0.01 and 0% by mass). Monomers d) are preferably α, β-ethylenically unsaturated C₃ ~ C₆ Monocarboxylic acids, such as acrylic acid or methacrylic acid, and monoethylenically unsaturated C₄ ~ C₈ Dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid and citraconic acid. Suitable monomers d) are further ethylenically unsaturated monomers having sulfonic acid groups, such as vinyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 2-acryloxyethanesulfonic acid and 2-methacryloxyethanesulfonic acid. Salts thereof, preferably ammonium salts thereof, in particular ammonium salts which are non-volatile at room temperature, and preferably alkali metal salts thereof, in particular sodium salts. Preference is given to acrylic acid and methacrylic acid.
[0024]
The copolymer advantageously comprises less than 4% by weight of ethylenically unsaturated nitrile, such as acrylonitrile or methacrylonitrile. Particularly preferably, the copolymers are substantially free of such nitriles or they have an amount of 0.1 to at most 3.5% by weight. The low content of nitrile polymerized together is advantageous for the low water absorption of building materials modified according to the invention.
[0025]
The copolymer advantageously comprises less than 0.5% by weight of an amide of α, β-unsaturated monocarboxylic acid and dicarboxylic acid. Particularly preferably, the polymer dispersion used according to the invention is free or substantially free of amides of carboxylic acids. The lowest possible content of amides of α, β-ethylenically unsaturated carboxylic acids is advantageous for the low odor generation of the dispersions according to the invention in the presence of hydraulic binders.
[0026]
In addition, the copolymer can include small amounts of other monomers, such as those conventionally used in the manufacture of aqueous polymer dispersions.
[0027]
Suitable other comonomers are, for example, silicon-containing monomers, in particular monomers having silyl groups, such as vinyltrialkoxysilanes, such as vinyltrimethoxysilane, alkylvinyldialkoxysilanes or (meth) acryloxyalkyltrialkoxysilanes, such as (Meth) acryloxyethyltrimethoxysilane, (meth) acryloxypropyltrimethoxysilane and trimethoxysilylpropyl methacrylate, monomers having a glycidyl group, especially glycidyl (meth) acrylate, glycidyl vinyl ether, 1,3-diketo group Monomers, especially acetoxyethyl (meth) acrylate and diacetone (meth) acrylamide, monomers having urea groups, such as ureidoethyl (meth) acrylate It is more acrylamido glycolic acid and methacrylamide glycolate methyl ester. When these other comonomers are included in the polymer dispersion used according to the invention, they are usually present in an amount of 0.1 to 10% by weight, preferably not exceeding 5% by weight in the copolymer. Are polymerized together.
[0028]
Particularly advantageously,
a) at least one monomer selected from ethyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate a) 55-80% by weight and in particular 60-76% by weight,
b) Styrene and / or methyl methacrylate 12-35% by weight, in particular 15-30% by weight,
c) C₂ ~ C₆ An alkanediol, preferably C₂ ~ C₄ 3-12% by weight of at least one monoester of alkanediol and acrylic acid or methacrylic acid, preferably acrylic acid, in particular 3-9% by weight, for example about 4, about 6 or about 8% by weight, And possibly
d) Less than 1% by weight, preferably 0.1-1% by weight of at least one ethylenically unsaturated carboxylic acid selected from acrylic acid, methacrylic acid, maleic acid and itaconic acid, preferably acrylic acid and methacrylic acid %, In particular 0.2 to 1% by weight,
Is a copolymer that is polymerized together. Particularly preferably, the copolymer does not contain further primary amino groups and / or nitrile groups. In another embodiment, the copolymer does not contain the monomer d) containing acid groups and contains the monomers a), b) and c) in the above amounts and advantageously in the amounts described as advantageous. .
[0029]
In an advantageous embodiment of the invention, the copolymer contains only vinyl aromatics, in particular styrene, as monomer b), which in particular is a copolymer with at least one acid group. This is particularly true when the polymerized ethylenically unsaturated monomer (monomer d) is substantially not included.
[0030]
The copolymers used are known, commercially available or can be prepared by known methods.
[0031]
The production of the copolymer is usually carried out by a radical, aqueous emulsion polymerization in the presence of at least one radical polymerization initiator and optionally one or more surfactants.
[0032]
The aqueous emulsion polymerization can be carried out according to a conventional method, for example, “Encyclopedia of Polymer Science and Technology”, Vol. 5, Wiley & Sons Inc., NY 1966, p. 847). A copolymer dispersed in water in the form of multiphase particles can also be used. The production can be carried out in a sequential manner, for example by the methods described in the specifications of European Patent (EP) 555959, European Patent (EP) 308753 and European Patent (EP) 654454.
[0033]
The polymerization is carried out by a usual method in the presence of a radical-forming compound (initiator). These compounds are preferably used in an amount of 0.05 to 10, particularly preferably 0.5 to 5% by weight, based on the monomers used in the polymerization.
[0034]
Further, a polymer copolymer polymerized in the presence of a conventional crosslinking agent can also be used. Suitable cross-linking agents are known to the expert, for example from DE 19729161.9, which is hereby incorporated by reference in its entirety.
[0035]
Suitable surfactants for carrying out the emulsion polymerization are protective colloids and emulsifiers usually used for this purpose. The surface-active substance is usually used in an amount of not more than 10% by weight, preferably 0.1 to 7.5% by weight and in particular 1 to 5% by weight, based on the monomer to be polymerized.
[0036]
Suitable protective colloids are, for example, copolymers comprising polyvinyl alcohol, starch derivatives and cellulose derivatives or vinyl pyrrolidone. A detailed description of other suitable protective colloids can be found in Hoben-Weyl, Methoden der organischen Chemie, Band XIV / I, Macromolekulare Stoffe, Georg- Thieme-Verlag, Stuttgart 1961) 411-420. Mixtures of emulsifiers and / or protective colloids can also be used.
[0037]
Advantageously, no protective colloid is used in the production of the copolymer. If the polymer dispersion contains a protective colloid, this is preferably added only after the preparation of the polymer dispersion.
[0038]
Particularly preferably, only emulsifiers having a relative molecular weight of usually 2000 or less are used as surfactants, unlike the protective colloids. These can be anionic, cationic or nonionic. The emulsifiers used within the scope of the present invention are preferably nonionic or anionic emulsifiers. Although nonionic emulsifiers are usually nonionic alkoxylated emulsifiers, anionic emulsifiers distinguish between anionic nonalkoxylated emulsifiers and anionic alkoxylated emulsifiers in the following.
[0039]
Anionic non-alkoxylated emulsifiers include alkyl sulfates (alkyl groups: C₈ ~ C₄₀), Eg sulfuric acid half ester, C₈ ~ C₂₂-Fatty alcohol or C₈ ~ C₃₂-Oxo alcohol, alkylsulfonic acid (alkyl group: C₁₂~ C₁₈), Sulfosuccinic acid di-C₆ ~ C₂₅-Alkyl esters and alkylaryl sulfonic acids (alkyl group: C₆ ~ C₃₂), For example C₆ ~ C₃₂-Alkali metal alkali salts and ammonium salts of alkylphenols. Other suitable emulsifiers are Hoben-Weyl, Method of Organic Chemistry, Volume XIV / 1, Polymeric Materials (Houben-Weyl, Methoden der organischen Chemie, Band XIV / I, Macromolekulare Stoffe, Georg-Thieme-Verlag, Stuttgart 1961) pp. 192-208.
[0040]
Anionic non-alkoxylated emulsifiers also have the general formula I
[0041]
[Chemical 1]

[0042]
[In the formula, R¹ And R² Is hydrogen or C₄ ~ C₂₄-Represents alkyl and is not simultaneously hydrogen, and X and Y may be alkali metal ions and / or ammonium ions. X and Y are preferably sodium, potassium or ammonium, with sodium being particularly preferred. Often industrial mixtures having a proportion of 50 to 90% by weight of the monoalkylated product, such as Dowfax^(R) 2A1 (trade name of Dow Chemical Company) is also used. Compound I is generally known, for example, from US Pat. No. 4,269,749 and is commercially available.
[0043]
For use according to the invention, preference is given to polymer dispersions comprising alkoxylated emulsifiers, in particular nonionic alkoxylated emulsifiers and / or anionic alkoxylated emulsifiers. Alkoxylated emulsifiers are also treated with the copolymers used according to the invention, for example the mixing and processing properties of the copolymers and hydraulic binders and the acceptability of the polymers and hydraulic binders. The handling and mechanical properties of the binder are also improved.
[0044]
Alkoxylated emulsifiers are emulsifiers having oligoalkylene oxide units or polyalkylene oxide units in the hydrophilic part. Usually, the alkoxylated emulsifier is obtained by reacting a lipophilic compound or compounds having a lipophilic group with an alkylene oxide, in particular ethylene oxide and / or propylene oxide. Such alkoxylated emulsifiers may additionally be modified with ionic, in particular anionic groups. Accordingly, an anionic alkoxylated emulsifier having at least one anionic or anionic group is distinguished from a nonionic alkoxylated emulsifier without such a group.
[0045]
Examples of lipophilic compounds or compounds having a lipophilic group are aliphatic, aromatic and / or araliphatic alcohols, amides, amines and carboxylic acids and derivatives thereof. Advantageously, the lipophilic compound or compounds having a lipophilic group are fatty acids, fatty alcohols, oxoalcohols, amines, amides and salts derived therefrom, phenols, alkylphenols, hydroxynaphthalenes or aminonaphthalenes, dicarboxylic acids and Random copolymers comprising these esters or half-esters and polyalkylene oxides having a lipophilic or lipophilic moiety having at least one hydroxyl group, such as polypropylene oxide, polybutylene oxide and ethylene oxide, propylene oxide and / or butylene oxide Or it is a block copolymer.
[0046]
The degree of alkoxylation of such alkoxylated emulsifiers is usually in the range from 2 to 150, preferably from 3 to 100 and particularly preferably from 4 to 50.
[0047]
Examples of preferred nonionic aliphatic alkoxylated emulsifiers are ethoxylated or ethoxylated / propoxylated, preferably ethoxylated C, having a degree of alkoxylation of 3-100, preferably 4-50.₆ ~ C₃₂Fatty alcohols and C₆ ~ C₃₂-Fatty amine, C₆ ~ C₆₀-Oxo alcohols and C₆ ~ C₆₀-Amine, linear primary C₆ ~ C₆₀Ziegler Alcohols, fatty acid alkylolamides, fatty acids and fatty acid amides and polyalkylene oxide adducts, such as ethylene oxide-propylene oxide block copolymers.
[0048]
Preferred nonionic aliphatic alkoxylated emulsifiers are ethoxylated C₆ ~ C₃₂Fatty alcohols, preferably C₈ ~ C₂₀A fatty alcohol, in particular C₉ ~ C₁₆-Fatty alcohols, for example, almost unbranched fatty alcohols obtained by reduction of naturally occurring fatty acids, and ethoxylated C which are generally more branched compared to fatty alcohols₆ ~ C₃₂An oxo alcohol, preferably C₈ ~ C₂₀Oxo alcohols and in particular C₉ ~ C₁₆An oxo alcohol having an average degree of ethoxylation of 2 to 150, preferably 4 to 50, in particular 6 to 30, for example 8 to 15 or 12 to 25. Examples of advantageous nonionic aliphatic alkoxylated emulsifiers are ethoxylated lauryl alcohols having a degree of ethoxylation of 4 to 50, in particular 8 to 25, for example LUTENSOL of the BASF Corporation Lutensolmarken.^(R) AT18 and AT25.
[0049]
Examples of nonionic aromatic or aromatic-aliphatic alkoxylated emulsifiers are ethoxylated and ethoxylated / propoxylated having an average degree of alkoxylation of 2-150, preferably 3-100 and especially 3-50, Preferably ethoxylated C₆ ~ C₃₂-Alkylphenols, in particular C₆ ~ C₁₆-Alkylphenol.
[0050]
The anionic group of the anionic alkoxylated emulsifier is usually selected from sulfuric acid group, sulfonic acid group, carboxylic acid group, phosphonic acid group and phosphoric acid group. Preferred as the counter ion of the anionic group are cations such as sodium ion, potassium ion, calcium ion or ammonium ion, and mixtures thereof. Advantageously, the counterion different from the ammonium ion is a lightly volatile amine, such as ammonia, methylamine or ethylamine, the preferred counterion being a sodium ion. Preferred anionic groups are sulfuric acid groups and sulfonic acid groups.
[0051]
Examples of anionic alkoxylated emulsifiers are sulfuric acid half esters and phosphoric acid monoesters of the above nonionic alkoxylated emulsifiers, and C₈ ~ C₃₂-Alkenyl polyethoxysulfonates and C₈ ~ C₃₂-Alkenyl polyethoxy sulfate, C₈ ~ C₃₂Alkyl glyceryl polyethoxysulfonates, ethoxylated sulfosuccinic acid half esters and ethoxylated sulfosuccinic acid diesters, C₈ ~ C₃₂Alkenyl polyethoxy phosphates or dialkyl polyethoxy phosphates, ethoxylated one- or multiple-nucleated monoalkyl and dialkyl biphenyl ethers, dialkyl biphenyl ethers, ethoxylated α-sulfo fatty acid esters, ethoxylated fatty acid alkanolamine sulfates Sulfonated or sulfated ethoxylated fatty acid esters, fatty acid sarcosides, fatty acid glycolates, fatty acid lactates, fatty acid taurides and fatty acid isothionates, which are 2 to 150, preferably 2 to 100 and particularly preferably 3 to 50. And their salts, especially alkali metal salts such as sodium or potassium salts, or ammonium salts, organic amines such as mono-C₁ ~ C₄ -Alkylamines, di-C₁ ~ C₄ -Alkylamine or tri-C₁ ~ C₄ -Salts with alkylamines or monoethanolamine, diethanolamine or triethanolamine.
[0052]
Preferred anionic aliphatic alkoxylated emulsifiers are ethoxylated C₈ ~ C₂₀A fatty alcohol, in particular C₉ ~ C₁₆-Fatty alcohols, for example sulfuric acid half esters of almost unbranched fatty alcohols obtained by reduction of naturally occurring fatty acids, and ethoxylated C which are generally more branched compared to fatty alcohols₈ ~ C₃₂Oxo alcohols, in particular C₉ ~ C₁₆Oxo alcohols having an average degree of ethoxylation of 2 to 50, in particular 2 to 30, for example 2 to 15 or 9 to 30.
[0053]
Preferred anionic aromatic or anionic aromatic-aliphatic alkoxylated emulsifiers are ethoxylated and ethoxylated / propoxylated, preferably ethoxylated C₆ ~ C₃₂-Alkylphenols, in particular C₆ ~ C₁₆Alkylphenols and particularly preferably octylphenols and nonylphenol sulfate half-esters having an average degree of alkoxylation in the range of 2-50, in particular 2-35.
[0054]
Optionally, the preparation according to the invention can also comprise non-alkoxylated emulsifiers, but usually at least 50% by weight, preferably at least 75% by weight, of the emulsifiers used are alkoxylated emulsifiers. In one embodiment, the preparation according to the invention is substantially free of non-alkoxylated emulsifiers. Another advantageous embodiment relates to a preparation comprising at least one nonionic alkoxylated emulsifier and at least one anionic emulsifier selected from alkoxylated and anionic nonalkoxylated emulsifiers.
[0055]
Advantageously, the polymer dispersion used according to the invention or a polymer powder obtained by drying therefrom, ie by removing at least 80%, preferably at least 85% or at least 90% by weight of the volatile constituents or The polymer granules comprise 0.2 to 10% by weight and preferably 0.5 to 5% by weight of at least one emulsifier, based on the polymer content.
[0056]
In an advantageous embodiment of the invention, at least one nonionic alkoxylated emulsifier, preferably a nonionic aliphatic alkoxylated emulsifier, is used as the alkoxylated emulsifier.
[0057]
Advantageously, the polymer used according to the invention is
A mixture of at least one nonionic alkoxylated emulsifier and at least one anionic alkoxylated emulsifier, or
A mixture of at least one nonionic alkoxylated emulsifier, at least one anionic alkoxylated emulsifier and at least one anionic nonalkoxylated emulsifier, or
A mixture of at least one anionic non-alkoxylated emulsifier and at least one non-ionic alkoxylated emulsifier
including.
[0058]
Polymer dispersions containing a mixture of such emulsifiers are particularly characterized by a further increased stability against shear loads.
[0059]
If the copolymer used according to the invention comprises a mixture of at least one anionic emulsifier and at least one nonionic alkoxylated emulsifier, the total amount of emulsifier contained is usually 15 to 90% by weight, preferably 25-80% by weight and in particular 40-70% by weight, are allocated to the anionic emulsifier.
[0060]
Particularly preferred emulsifier mixtures according to the invention are at least one nonionic aliphatic alkoxylated emulsifier, preferably ethoxylated C₈ ~ C₂₀A fatty alcohol, in particular C₉ ~ C₁₆Fatty alcohols and / or ethoxylated C₈ ~ C₃₂Oxo alcohols, in particular C₉ ~ C₁₆Oxo alcohols having an average degree of ethoxylation of 5 to 50, in particular 6 to 30 and at least one anionic aliphatic alkoxylated emulsifier, preferably ethoxylated C₈ ~ C₂₀A fatty alcohol, in particular C₉ ~ C₁₆-Sulfuric acid half esters of fatty alcohols and / or ethoxylated C₈ ~ C₃₂Oxo alcohols, in particular C₉ ~ C₁₆-Sulfuric acid half esters of oxo alcohols having an average degree of ethoxylation of 2 to 50, in particular 3 to 35.
[0061]
The above-mentioned surface active substances, in particular emulsifiers, are used in whole or in part during the production of the copolymer and are added in whole or part after the production of the copolymer, or in whole or part in the building according to the invention. It can be added in use for the production of materials. In the production of the copolymers used according to the invention by radical emulsion polymerization in an aqueous medium, at least 25% by weight, preferably at least 35% by weight and particularly preferably at least 50% by weight, of the total amount of emulsifier. It has proven advantageous for use in the production of copolymers.
[0062]
In some embodiments, the entire amount of emulsifier is used in the production of the copolymer. In another advantageous embodiment, 30 to 65% by weight, preferably 35 to 60% by weight and particularly preferably 40 to 55% by weight of the total amount of ionic emulsifier used are preferably used for radical emulsion polymerization. Add in the process. The remaining amount of the emulsifier is added after completion of the polymerization (post-saponification). For production and “post-saponification”, the same or different emulsifiers can be added, in the case of the addition of several emulsifiers, the mixing ratio of the emulsifiers for the production of the copolymer and for post-saponification Because of it can be different. In particular, an anionic alkoxylated emulsifier and / or an anionic non-alkoxylated emulsifier can be used in the post-saponification.
[0063]
In order to achieve a sufficient improvement in the mechanical strength of building materials based on hydraulic binders, it is usually recommended to use copolymers having a glass transition temperature of -60 ° C or higher, preferably -50 ° C or higher. The Thus, the copolymer is preferably a glass transition temperature T_g It has> -45 ° C, particularly preferably> -40 ° C and in particular> -35 ° C.
[0064]
In order to achieve a sufficient improvement in the flexibility of building materials, in particular the low temperature flexibility, the copolymers in building materials based on hydraulic binders had to be able to be filmed. Thus, the copolymers used according to the invention are usually <+ 40 ° C., in particular <+ 30 ° C., particularly preferably <+ 20 ° C., particularly preferably <+ 10 ° C. and in particular <+ 0 ° C. Glass transition temperature T_g Have
[0065]
Accordingly, copolymers suitable for use according to the present invention have glass transition temperatures T of about -30 ° C, about -25 ° C, about -20 ° C, about -15 ° C, about -10 ° C or about -5 ° C._g Have
[0066]
Glass transition temperature T_g As understood herein as “midpoint temperature” as measured by differential thermal analysis (DTA) according to ASTM D3418-82 (Ullmann's Encyclopedia of Industrial Chemistry, 5th edition). , 5th Edition, Volume A21, VCH Weinheim, 1992), page 169 and Sozel (Zosel, Farbe und Lack 82 (1976), S. 125-134), see also DIN 53765).
[0067]
In a polymer dispersion containing copolymer components having different glass transition temperatures, usually, a glass transition temperature T at least a major portion of which falls within the above range._g It is advantageous when it has. Such preparations can be made, for example, by mixing two or more different copolymers or into, for example, multi-stage polymers, polymer particles having a core-shell structure or other non-random composition. Obtained by the leading polymerization method.
[0068]
Glass transition temperature T to desired value_g This adjustment can be carried out by selecting the corresponding monomer and also by selecting the proportion of the monomers used in the copolymer or several copolymers.
[0069]
In this context, the glass transition temperature T of the copolymer P_g It has been found useful to estimate Fox (TG Fox, Bull. Am. Phys. Soc. (Ser. II) 1, 123 (1956)) and Ullmanns Enzyklopaedie der technischen Chemie, Weinhein (1980), pages 17-18 According to, the glass transition temperature of the weakly crosslinked copolymer is a good approximation at high molecular weight,
[0070]
[Expression 1]

[0071]
[Where X¹ , X² ... Xⁿ Is the mass fraction of monomers 1, 2,..., N, and T_g ¹ , T_g ² ... T_g ⁿ Represents a single absolute temperature display glass transition temperature of a polymer composed of one type of each of monomers 1, 2,..., N]. For example, Ullmann's Encyclopedia of Industrial Chemistry, VCH Weinheim, Volume A21, 1992, page 169 of Ullmann's “Encyclopedia of Industrial Chemistry” or Brand Wrap et al. (J. Brandrup, EH Immergut, Polymer Handbook 3rd. Ed. J. Wiley, New York, 1989).
[0072]
The method for adjusting the particle size of the polymer is, for example, European Patent Application Publication (EP-A) No. 126699, European Patent Application Publication (EP-A) No. 567881, European Patent Application Publication (EP-A) No. 567819. German Patent Application Publication (DE-A) 3147008 and German Patent Application Publication (DE-A) 4213967.
[0073]
The polymer dispersion used according to the invention is preferably 6.7 to 8.0, preferably 6.8 to 7.5 and particularly preferably 6.9 to 7.2, for example 7.0. For adjusting the pH value of the polymer dispersion having a pH value in the range of ˜7.1, a non-volatile base is preferably used. Suitable non-volatile bases are, for example, caustic soda, caustic and lime milk which can be used, for example, as a solid or as an aqueous solution (calcium hydroxide solution). Advantageously, lime milk is used as an aqueous suspension. The maintenance of the specific pH range described above and the use of the bases advantageously affect the range of use of the dispersions used according to the invention. In particular, the acceptability of the polymer dispersion and the hydraulic binder has an advantageous effect.
[0074]
The polymer dispersions used according to the invention are based on hydraulic binders directly, optionally after adjustment of the solids content and / or after addition of customary auxiliary substances (such as those described below). Can be added to the material. When aqueous dispersions are used according to the invention, the solids content of the dispersion, i.e. the proportion of non-volatile components, is usually in the range of 20 to 80% by weight. The dispersion preferably uses an aqueous dispersion of 30 to 70% by weight, in particular 35 to 60% by weight and particularly preferably 40 to 55% by weight, based on the solids content.
[0075]
The viscosity of the aqueous dispersion was 55 ° C. using a rotational viscometer according to DIN 53019 at 23 ° C. and a shear rate of 250 s.^{- 1}In the range of 10 to 2500 mPas, preferably 20 to 500 mPas. The aqueous polymer dispersion may contain organic solvents, preferably organic solvents miscible with water, such as alcohols, diols and polyols. The content of the organic solvent is preferably less than 10% by weight, based on the total weight of the polymer dispersion, particularly preferably the polymer dispersion is substantially free of organic solvent.
[0076]
The polymer dispersions used according to the invention can also be used in the form of half esters, for example pasty substances, or in solid form, for example powders or granules. The polymer powder or polymer granules are obtained from the polymer dispersion by drying, preferably by spray drying.
[0077]
The subject of the present invention is therefore an inorganic substance based on a hydraulic binder of a polymer powder or polymer granules obtained by removing at least 80% by weight, preferably at least 90% by weight, of the volatile constituents from the above polymer dispersion. It is also used as an admixture in building materials.
[0078]
The polymer dispersion, polymer powder or polymer granule can contain conventional auxiliaries. The auxiliaries are generally used in an amount of 0.1 to 30% by mass in total with respect to the copolymer. Conventional auxiliaries are, for example, wetting agents, bactericides, biocides, antifoaming agents such as BASF (Ludwigshafen), Munchich (Heilbronn) and Wacker (Munich). ) (Fa. Wacker (Muenchen)) defoamers, thickeners, antifreezes, leveling agents, softeners and film forming aids available on the market. Suitable film forming aids are, for example, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, dibutylene glycol, these C₁ ~ C₄ Semi-ethers with alkanols, such as diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monophenyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, these ethers -Acetates such as diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate, propylene glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate, dipropylene glycol-n-butyl ether acetate, and also aliphatic monocarboxylic acids and dicarbohydrates Alkyl esters of acids, for example, Eastman Kodak Texanol the (Eastman Kodak) (Texanol)^(R) Or an industrial mixture thereof, for example, Lusolvan from BASF Corporation^(R) FBH (a di-n-butyl ester mixture of succinic acid, glutaric acid and adipic acid). As a softener, all conventional and suitable softeners for dispersions, for example (oligo) propylene glycol alkylphenyl ethers, such as Plastilit from BASF Corporation^(R) 3060 is available on the market and is relevant.
[0079]
The polymer dispersion, polymer powder or polymer granule used according to the invention can additionally contain a liquefaction agent (Verfluessiger) for the hydraulic binder. Usually, liquefaction agents for hydraulic binders are additives for changing the properties of building materials based on hydraulic binders, in particular processability and / or bondability. Usually such liquefying agents for building materials based on hydraulic binders are water-soluble polymeric substances.
[0080]
The good processability of building materials based on hydraulic binders modified with the dispersion used according to the invention can be further improved in many cases by the presence of liquefaction agents.
[0081]
Preferably based on naphthalenesulfonic acid-formaldehyde-condensates, melamine-formaldehyde-polycondensates and / or lignin sulfonates, such as those described in EP-A 402 319, And those based on homopolymers and copolymers of carboxylic acids and dicarboxylic acids with styrene, such as EP-A 306449 and US-A 3952805, or isobutane or With diisobutane, for example, German Patent Application Publication (DE-A) 3716974, European Patent Application Publication (EP-A) 338293, German Patent Application Publication (DE-A) 3925306 U.S. Pat. No. 4,586,960 Saisho, U.S. Patent (US-A) liquefying agent according to the 4,042,407 Patent specification and U.S. Patent (US-A) Specification No. 4,906,298 are preferred.
[0082]
Similarly, based on copolymers of unsaturated carboxylic acids and hydroxyalkyl esters of unsaturated carboxylic acids, such as those described in European Patent (EP) 97613, copolymerized carboxylic acid monomers and acrylic acid and Based on polyalkylene oxide esters of methacrylic acid, for example those described in German Offenlegungsschrift DE-A 4420444, ethylenically unsaturated polyoxyalkylene ethers, multi-unsaturated alkenyl ethers and maleic anhydride, For example, based on those described in European Patent (EP) 619277 or copolymers of maleic acid derivatives and vinyl monomers, eg German Patent Application Publication (DE-A) 4304109 and European Patent Application Publication ( EP-A) described in No. 610699 Liquefying agents based on those are also suitable.
[0083]
The above publications are hereby incorporated by reference in their entirety.
[0084]
Such liquefying agents are, for example, ADDIMENT (Heideiberg), SKW (Trostberg), BASF (Ludwigshafen), in particular the Sokalan trademark, and DYCHERHOFF (Wisbaden). Wiesbaden)).
[0085]
Preference is given to using liquefying agents based on naphthalenesulfonic acid condensates, carboxylic acid monomer copolymers, polyalkylene oxide esters of acrylic acid and methacrylic acid.
[0086]
The copolymers used according to the invention, i.e. polymer dispersions, polymer powders or polymer granules, are calculated as copolymers in building materials based on hydraulic binders, and relative to the dry mass of hydraulic binders, Preference is given to using amounts of 5 to 250% by weight, particularly preferably 10 to 150% by weight and in particular 20 to 100% by weight. Usually, to achieve the desired property improvement of building materials based on hydraulic binders and hydraulic binders, it is admixed with 10-50% polymer or 15-40% polymer by weight in hydraulic binders. Enough.
[0087]
The polymer dispersions, polymer powders or polymer granules used according to the invention are usually calculated as a copolymer on a building material based on a hydraulic binder and are 2 to 2 with respect to the dry mass of the inorganic component of the building material. An amount of 150% by weight, preferably 5-80% by weight and particularly preferably 10-50% by weight, is added. Usually, the addition of 5 to 35% by weight or 10 to 25% by weight of polymer is sufficient relative to the dry weight of the inorganic component of the building material based on hydraulic binder to achieve the desired property improvement of the building material. It is.
[0088]
Conventional auxiliaries for building materials based on hydraulic binders are in particular the auxiliaries and liquefiers mentioned above. Suitable other auxiliaries for use in building materials are known to the expert, for example H.P. Royle "Handbook of Architectural Chemistry" (H. Reul, Handbuch der Bauchemie, Verlag fuer chemische Industrie, H. Ziolkowsky KG, Augsburg (1991)).
[0089]
Conventional additives for building materials based on hydraulic binders include, for example, inorganic additives such as gravel, coarse sand, fine sand, quartz sand of various sizes, eg 0.08 to 0.8 mm particle size , Quartz powder, eg particle size ≦ 0.09 mm, basalt, limestone, chalk, marble, truss, silica sand, precipitated silicic acid, coal fly ash and barium sulfate or non-inorganic additives, eg organic fibers or organic porous materials Is applicable. Other suitable inorganic or non-inorganic additives are known to the expert, e.g. the German Architectural Chemistry Status Report `` Modified Inorganic Mortar System and Environment '' (Sachstandsbericht Dt. Bauchemie: Modifizierte Mineralische Moertalsysteme and Umwelt (1. Ausgabe, Juli 1998)).
[0090]
Similarly, the object of the present invention is to calculate the above-mentioned polymer dispersion, polymer powder or polymer granule obtained therefrom as a copolymer, and preferably 2 to 150% by weight, preferably based on the dry weight of the inorganic component. Comprises building materials based on hydraulic binders comprising 5 to 80% by weight and particularly preferably 5 to 30% by weight.
[0091]
Typical building materials based on hydraulic binders whose properties can be improved by use according to the invention are cement, liquid cement, concrete, mortar, plaster, swab, binder preparations, especially those based on cement, road surfaces Pavement and tile adhesive. An advantageous building material is in particular an inorganic sealant.
[0092]
Building materials may exist in solid form (eg before addition of formulation water and polymer dispersion or after curing), in liquid form and in high-viscosity liquid or porous form, depending on the intended use and processing stage. it can.
[0093]
Of course, the polymer powder obtained from the polymer dispersion can be mixed with an inorganic binder before use in building materials. Such preparations usually contain hydraulic binders, preferably cement, and polymers as main components. In addition, these preparations can contain customary inorganic or non-mineral additives and customary auxiliaries such as those mentioned above.
[0094]
Furthermore, the present invention relates to the mechanical strength, elasticity and elasticity of building materials based on hydraulic binders mixed together with hydraulic binders and polymer dispersions, polymer powders or polymer granules and optionally water and / or additives. The present invention relates to a method for improving workability. Suitable mixing techniques and equipment are known to the expert and are described, for example, in Ullmann “Industrial Chemical Encyclopedia” 3rd Edition, 1951, Volume 1, pages 693-727.
[0095]
The use according to the invention of polymer dispersions, polymer powders or polymer granules is uncomfortable during and after mixing of the polymer with the hydraulic binder compared to polymer modified building materials based on prior art hydraulic binders. Resulting in a polymer-dispersed suspension-dispersing material characterized in that it produces no or only a slight odor. The use according to the invention of polymer dispersions, polymer powders or polymer granules can further be achieved in a number of building materials based on inorganic binders, with improved properties in solidified or bonded state, in particular high mechanical strength, for example Provides high flexibility, high breaking strength and / or high cohesive strength. The water resistance of the solidified or bonded building material is improved and its water absorption is significantly reduced. Usually, the workability of building materials based on hydraulic binders prior to solidification is also determined, for example, by advantageous so-called “pot life” and mixing or slurrying hydraulic binders into liquid, semi-solid or pasty building materials. Improved by low adhesion or sticking to the mold during the process. The properties of the dispersions, polymer powders or granules according to the invention are particularly preferably used for building materials based on cement.
[0096]
The polymer dispersions according to the invention are of course used in non-cement systems, in particular in coating systems containing fillers, in particular flexible coating systems such as flexible roofing materials and sealing materials and adhesives, in particular fillers. Suitable for building adhesives such as tile adhesives.
[0097]
A typical formulation of a flexible roof covering material comprises the polymer dispersion according to the invention in addition to water. Pigments such as titanium dioxide or barium sulfate and fillers such as calcium carbonate, chalk, talc, clay and conventional auxiliaries such as biocides, wetting agents, film-forming auxiliaries such as hydrocarbons such as gasoline, softeners, solvents and Antifreeze agents such as glycerin or glycols, thickeners (eg associative thickeners) and antifoam agents. The proportion of the pigment is usually in the range of 1 to 5 parts by weight with respect to 1 part by weight of the copolymer. The proportion of the auxiliary agent is usually in the range of 0.5 to 25 parts by weight with respect to 100 parts by weight of the copolymer.
[0098]
A typical composition of a flexible roof covering material coating is described in Example 2 of EP-A 501272 cited herein, in which the polymer dispersion described therein is referred to Replace with the polymer dispersion according to the invention. Another blend of flexible roof coverings is described in L.L. Described in Chander (L. Chander, Paint & Resin 9/10, 1981, pages 24-25), in which case the polymer dispersion used is likewise replaced by the copolymer dispersion according to the invention. Can do.
[0099]
Typical formulations of tile adhesives include, in addition to the copolymers according to the invention and water, also fillers, such as the fillers and / or silicates mentioned above, or silicic acids, and also auxiliary substances such as those mentioned above. Includes auxiliary materials. The ratio of a filler is 5-10 mass parts normally with respect to 1 mass part of copolymers. The ratio of the auxiliary material is usually 1 to 20 parts by mass with respect to 100 parts by mass of the copolymer. Representative formulations of tile adhesives are described in Examples 2 and 4 of European Patent Application Publication (EP-A) 35322 cited herein. The polymer dispersion described here can be exchanged for the copolymer-dispersion according to the invention.
[0100]
The following examples illustrate the invention without limiting it.
[0101]
【Example】
The polymer dispersion according to the present invention and the polymer dispersion of the comparative example used in the examples of the present invention were obtained by radical polymerization in an aqueous medium.
[0102]
A list expressed in mass% of monomers polymerized together in the copolymer of the polymer dispersion is given in Table 1. The solids content of the polymer dispersion (i.e., the non-volatile portion) was measured from the mass loss (about 1 g) of the sample by drying at 120 ° C. for 2 hours in an air circulating dryer. The viscosity of the polymer dispersion was measured using a rotational viscosity meter (Rheomat) from Firm Paar Physica according to DIN 53019 at 23 ° C. and a shear rate of 250-1. Glass transition temperature T_g Was measured using a differential calorimeter DSC820 from Fa. Mettler Toledo at a linear heating rate of 5 ° C./min.
[0103]
I. Production of polymer dispersions according to the invention
Dispersion ED1
In a 2 l glass container having an anchor type stirrer (120 rpm), 200 g of completely demineralized water was charged. At an internal temperature of 85 ° C., 5% by weight of the total amount of feed (Zulauf) 1 and 10% by weight of the total amount of feed 2 were added. The charge was allowed to initiate polymerization at 85 ° C. for 10 minutes. Subsequently, the remaining amount of feed 1 and feed 2 was added spatially separately in succession at 85 ° C. within 3.5 hours. The mixture was allowed to cool for a further 30 minutes and then cooled, and then the reaction mixture was neutralized with 20% by weight aqueous calcium hydroxide. Feed 3 was added with stirring. The preparation thus produced contained 49.8% by weight of non-volatile components and had a pH value of 7.2. The viscosity was 67 mPas. The copolymer contained in the dispersion has a glass transition temperature T of −14 ° C._g Had.
[0104]
Supply 1:
185 g of completely demineralized water
Ethoxylated lauryl alcohol sulfuric acid half ester having a degree of ethoxylation of about 30
30% by weight aqueous sodium salt solution (Fa. Henkel Disponyl
(Disponil) FES 77); In the following, emulsifier solution I 17 g
Ethoxylated C having a degree of ethoxylation of about 18₁₆/ C₁₈-20 of alcohol
Mass% aqueous solution; emulsifier solution II 13 g below
110 g of styrene
385 g of n-butyl acrylate
Acrylonitrile 17g
2-hydroxyethyl acrylate 33g
Methacrylic acid 6g
Supply 2:
60g of completely demineralized water
Sodium peroxodisulfate 2g
Supply 3:
Emulsifier solution I 8g
Emulsifier solution II 25g
Dispersion ED2
In a 2 l glass container having an anchor type stirrer (120 rpm), 320 g of completely demineralized water was charged. At an internal temperature of 85 ° C., 5% by weight of the total amount of feed 1 and 10% by weight of the total amount of feed 2 were added. The charge was allowed to initiate polymerization at 85 ° C. for 10 minutes. Subsequently, the remaining amount of feed 1 and feed 2 was added spatially separately in succession at 85 ° C. within 3.5 hours. The mixture was allowed to cool for a further 30 minutes and then cooled, and then the reaction mixture was neutralized with 20% by weight aqueous calcium hydroxide. Feed 3 was added with stirring. The dispersion thus prepared contained 49.2% by weight of non-volatile components and had a pH value of 7.0. The viscosity was 46 mPas. The copolymer contained in the dispersion has a glass transition temperature T of −20 ° C._g Had.
[0105]
Supply 1:
371 g of completely demineralized water
Emulsifier solution I 30g
Emulsifier solution II 23g
Styrene 180g
725 g of n-butyl acrylate
2-hydroxyethyl acrylate 90g
Methacrylic acid 5g
Supply 2:
120g of completely demineralized water
Sodium peroxodisulfate 4g
Supply 3:
Emulsifier solution I 14g
Emulsifier solution II 45g
Dispersion ED3
In a 4 l glass container having an anchor type stirrer (120 rpm), 450 g of completely demineralized water was charged. At an internal temperature of 85 ° C., 5% by weight of the total amount of feed 1 and 10% by weight of the total amount of feed 2 were added. The charge was allowed to initiate polymerization at 90 ° C. for 10 minutes. Subsequently, at 90 ° C., the remaining amount of feed 1 within 3 hours and feed 2 within 3.5 hours were added spatially separately. After standing at this temperature for a further 30 minutes, the reaction mixture was cooled and then neutralized with 20% by weight aqueous calcium hydroxide. The polymer dispersion thus prepared contained 54.9% by weight of non-volatile components and had a pH value of 7.0. The viscosity was 148 mPas. The included copolymer has a glass transition temperature T of −8 ° C._g Had.
[0106]
Supply 1:
Completely desalted water 539g
Sulfuric half ester of ethoxylated nonylphenol having a degree of ethoxylation of about 25
25% by weight aqueous solution of sodium salt, 28 g of emulsifier solution III below
Ethoxylated octylphenol sulfate half ester having a degree of ethoxylation of about 25
20% by weight aqueous solution of sodium salt of ru; emulsifier solution IV 20 g below
960 g of n-butyl acrylate
390 g of methyl methacrylate
135g of 2-hydroxyethyl acrylate
Acrylic acid 15g
Supply 2:
95g of completely demineralized water
Sodium peroxodisulfate 7g
Dispersion ED4
In a 4 l glass container having an anchor type stirrer (120 rpm), 450 g of completely demineralized water was charged. At an internal temperature of 85 ° C., 5% by weight of the total amount of feed 1 and 10% by weight of the total amount of feed 2 were added. The charge was allowed to initiate polymerization at 85 ° C. for 10 minutes. Subsequently, the remaining amounts of Feed 1 and Feed 2 were added spatially separately at 85 ° C. within 3.5 hours. After standing at this temperature for a further 30 minutes, the reaction mixture was cooled and then neutralized with 20% by weight aqueous calcium hydroxide. Feed 3 was added with stirring. The polymer dispersion thus produced contained 50.4% by weight of non-volatile components and had a pH value of 7.0. The viscosity was 45 mPas. The included copolymer has a glass transition temperature T of -31 ° C._g Had.
[0107]
Supply 1:
413 g of completely demineralized water
Emulsifier solution I 35g
Emulsifier solution II 26g
420 g of 2-ethylhexyl acrylate
420 g of n-butyl acrylate
Styrene 210g
63g of 2-hydroxyethyl acrylate
Supply 2:
90g of completely demineralized water
Sodium peroxodisulfate 4g
Supply 3:
Emulsifier solution I 18g
Emulsifier solution II 53g
Dispersion ED5
In a 4 l glass container having an anchor type stirrer (120 rpm), 450 g of completely demineralized water was charged. At an internal temperature of 85 ° C., 5% by weight of the total amount of feed 1 and 10% by weight of the total amount of feed 2 were added. The charge was allowed to initiate polymerization at 85 ° C. for 10 minutes. Subsequently, the remaining amounts of Feed 1 and Feed 2 were added spatially separately at 85 ° C. within 3.5 hours. After standing at this temperature for a further 30 minutes, the reaction mixture was cooled and then neutralized with 20% by weight aqueous calcium hydroxide. Feed 3 was added with stirring. The polymer dispersion thus produced contained 50.3% by mass of non-volatile components and had a pH value of 6.9. The viscosity was 44 mPas. The included copolymer has a glass transition temperature T of -26 ° C._g Had.
[0108]
Supply 1:
413 g of completely demineralized water
Emulsifier solution I 35g
Emulsifier solution II 26g
368 g of 2-ethylhexyl acrylate
420 g of n-butyl acrylate
263 g of styrene
63g of 2-hydroxyethyl acrylate
Supply 2:
90g of completely demineralized water
Sodium peroxodisulfate 4g
Supply 3:
Emulsifier solution I 18g
Emulsifier solution II 53g
Dispersion ED6
In a 2 l glass vessel having an anchor type stirrer (120 rpm), 250 g of completely demineralized water was charged. At an internal temperature of 85 ° C., 5% by weight of the total amount of feed 1 and 10% by weight of the total amount of feed 2 were added. The charge was allowed to initiate polymerization at 85 ° C. for 10 minutes. Subsequently, the remaining amounts of Feed 1 and Feed 2 were added spatially separately at 85 ° C. within 3.5 hours. After standing at this temperature for a further 30 minutes, the reaction mixture was cooled and then neutralized with 20% by weight aqueous calcium hydroxide. Feed 3 was added with stirring. The polymer dispersion thus prepared contained 50.3% by mass of non-volatile components and had a pH value of 7.0. The viscosity was 47 mPas. The included copolymer has a glass transition temperature T of −25 ° C._g Had.
[0109]
Supply 1:
250g of completely demineralized water
Emulsifier solution I 18g
Emulsifier solution II 14g
220g 2-ethylhexyl acrylate
193 g of n-butyl acrylate
Styrene 138g
2-hydroxyethyl acrylate 22g
Supply 2:
Complete desalted water 50g
Sodium peroxodisulfate 2g
Supply 3:
Emulsifier solution I 9g
Emulsifier solution II 28g
II. Production of comparative dispersion
Comparative dispersion VD1
280 g of completely demineralized water was charged into a 2 l glass container having an anchor type stirrer (120 rpm). At an internal temperature of 85 ° C., 5% by weight of the total amount of feed 1 and 10% by weight of the total amount of feed 2 were added. The charge was allowed to initiate polymerization at 85 ° C. for 10 minutes. Subsequently, the remaining amounts of Feed 1 and Feed 2 were added spatially separately at 85 ° C. within 3.5 hours. After standing at this temperature for a further 30 minutes, the reaction mixture was cooled and then neutralized with 20% by weight aqueous calcium hydroxide. Feed 3 was added with stirring. The polymer dispersion thus produced contained 50.3% by mass of non-volatile components and had a pH value of 7.2. The viscosity was 48 mPas. The included copolymer has a glass transition temperature T of −24 ° C._g Had.
[0110]
The following was used as feed 1:
116g of completely demineralized water
Emulsifier solution I 15g
Emulsifier solution II 23g
288 g of 2-ethylhexyl acrylate
72g of styrene
74g acrylonitrile
2-hydroxyethyl acrylate 38g
Methacrylic acid 7g
The following was used as feed 2:
100g of completely demineralized water
Sodium peroxodisulfate 3g
The following was used as feed 3:
Emulsifier solution I 8g
Emulsifier solution II 15g
Comparative dispersion VD2
In a 2 l glass container having an anchor type stirrer (120 rpm), 170 g of completely demineralized water was charged. At an internal temperature of 85 ° C., 5% by weight of the total amount of feed 1 and 10% by weight of the total amount of feed 2 were added. The charge was allowed to initiate polymerization at 85 ° C. for 10 minutes. Subsequently, the remaining amounts of Feed 1 and Feed 2 were added spatially separately at 85 ° C. within 3.5 hours. After standing at this temperature for a further 30 minutes, the reaction mixture was cooled and then neutralized with 20% by weight aqueous calcium hydroxide. Feed 3 was added with stirring. The polymer dispersion thus produced contained 48.9% by weight of non-volatile components and had a pH value of 7.0. The viscosity was 388 mPas. The included copolymer has a glass transition temperature T of −21 ° C._g Had.
[0111]
The following was used as feed 1:
Completely desalted water 197g
Emulsifier solution I 15g
Emulsifier solution II 11g
391 g of 2-ethylhexyl acrylate
176 g of styrene
Acrylonitrile 16g
Acrylamide 38g
Methacrylic acid 9g
The following was used as feed 2:
60g of completely demineralized water
Sodium peroxodisulfate 2g
The following was used as feed 3:
Emulsifier solution I 8g
Emulsifier solution II 23g
Comparative dispersion VD3
In a 4 l glass container having an anchor type stirrer (120 rpm), 500 g of completely demineralized water was charged. At an internal temperature of 85 ° C., 5% by weight of the total amount of feed 1 and 10% by weight of the total amount of feed 2 were added. The charge was allowed to initiate polymerization at 85 ° C. for 10 minutes. Subsequently, the remaining amounts of Feed 1 and Feed 2 were added spatially separately at 85 ° C. within 3.5 hours. After standing at this temperature for a further 30 minutes, the reaction mixture was cooled and then neutralized with 20% by weight aqueous calcium hydroxide. Feed 3 was added with stirring. The polymer dispersion thus produced contained 49.4% by weight of non-volatile components and had a pH value of 7.2. The viscosity was 298 mPas. The included copolymer has a glass transition temperature T of −20 ° C._g Had.
[0112]
The following was used as feed 1:
561 g of completely demineralized water
Emulsifier solution I 43g
Emulsifier solution II 33g
853 g of 2-ethylhexyl acrylate
Styrene 382g
Acrylonitrile 29g
118g of 2-hydroxyethyl acrylate
Methacrylic acid 88g
The following was used as feed 2:
120g of completely demineralized water
Sodium peroxodisulfate 5g
The following was used as feed 3:
Emulsifier solution I 22g
Emulsifier solution II 65g
Comparative dispersion VD4
The dispersion was manufactured in the same manner as the dispersion VD3.
[0113]
The following was used as feed 1:
399 g of completely demineralized water
140 g of 15% by weight aqueous solution of sodium dodecyl sulfate (emulsifier solution V)
928 g of 2-ethylhexyl acrylate
Styrene 433g
Acrylonitrile 39g
124g of 2-hydroxyethyl acrylate
Methacrylic acid 23g
The following was used as feed 2:
120g of completely demineralized water
Sodium peroxodisulfate 5g
The following was used as feed 3:
Emulsifier solution V 140g
The polymer dispersion thus prepared contained 50.0% by weight of non-volatile components and had a pH value of 6.9. The viscosity was 76 mPas. The included copolymer has a glass transition temperature T of −21 ° C._g Had.
[0114]
III. Stability testing
As a standard for the stability of the dispersion, aggregate formation, shear stability, and electrolyte stability were measured as follows.
[0115]
The tendency of aggregate formation during emulsion polymerization was measured by filtering the cooled and neutralized polymer dispersion through a Perlonsieb with a mesh of 45 μm. The stated condensation value represents the ratio of the filtration residue after surface drying to the total mass of the polymer dispersion.
[0116]
For the shear stability test, for each dispersion, the undiluted sample was sheared for 10 minutes at 10,000 revolutions / minute using Dispermat (VMA Getzmann GmbH). Subsequently, a small sample was coated on a glass support. For comparison, a small amount of unsheared load dispersion was also coated on the glass support and then tested by comparing the content of agglomerates as well as fine agglomerates (so-called “Strippen”). A sample was considered not shear stable when there was a significant increase in aggregate content as well as strip content compared to the loaded sample.
[0117]
For the electrolyte stability test, samples of the respective dispersions were tempered at 23 ° C. and then added dropwise to a stirred aqueous calcium chloride solution having a constant concentration (calcium chloride content 0.5-7. 50 g each of 5% by weight calcium chloride solution). Table 1 lists, for each dispersion, the calcium chloride concentration of the solution in which each dispersion sample was still stable.
[0118]
The results are summarized in Table 2.
[0119]
IV. Testing of applied technical properties
As a measure of the hydrophilicity of the polymer dispersion, the water absorption of the film from each polymer dispersion was tested. A polymer film having a dry layer thickness of about 750 μm was produced from each polymer dispersion by drying in a circulating dryer at 50 ° C. for 7 days. Test pieces, both 2 cm long and 1 cm wide, were cut from the film and then stored in water at room temperature for 24 hours. Subsequently, the test piece was superficially dried and weighed. The water absorption was calculated from the ratio of the film mass after storage in water and before.
[0120]
Cementitious materials modified with polymer dispersions were prepared for the measurement of application properties as admixtures for building materials based on hydraulic binders. For this purpose, 182 parts by weight of Portland cement PZ 45F (CEM I 42.5 R), 218 parts by weight of each polymer dispersion (adjusted to a solid content of 50% by weight), 53 parts by weight of water, quartz powder (particle size ≦ 0.09 mm) 149 parts by mass, quartz sand (particle size 0.08 to 0.2 mm) 164 parts by mass, quartz sand (particle size 0.2 to 0.5 mm) 218 parts by mass, defoaming agent Lumiten from BASF Corporation (Lumiten)^(R) 14 parts by mass of E-P3108 and the defoaming agent Agitan from Munchich^(R) 281 2 parts by weight were added together and mixed.
[0121]
After the addition and mixing of all the components, the so-called “pot life”, ie the time during which the cementitious material does not crack or the solid particles in the material can still be molded plastically, was measured. For use, the pot life is preferably more than 30 minutes.
[0122]
In order to determine the odor generation tendency, samples were taken immediately after the production of each polymer-modified cementitious material, and then heated in a dryer at 50 ° C. for 30 minutes in a closed container. Subsequently, an odor test was performed and ammonia formation was tested in the gas space within the container using wet pH paper.
[0123]
In order to test the strength and elasticity of the obtained cementitious material, a cement film having a wet layer thickness of 2 mm was prepared therefrom. The film was cured for 28 days under standard conditions (23 ° C., 50% relative humidity). Subsequently, according to DIN 53455, the tensile force and elongation at break of the film were measured using an automatic material testing device at a pulling rate of 100 mm / min. The results of applied technical tests are summarized in Table 2.
[0124]
In Table 1, the monomer composition of the copolymer contained in the dispersion was unified by mass%. Here, nBA is n-butyl acrylate, S is styrene, AN is acrylonitrile, HEA is 2-hydroxyethyl acrylate, MAS is methacrylic acid, EHA is 2-ethylhexyl acrylate, MMA is methyl methacrylate, AS is acrylic acid, MAN is Methacrylonitrile and AM represent acrylamide.
[0125]
Calculated as a solid, the emulsifier content relative to the copolymer was about 3% by weight in all dispersions except ED3. The emulsifier content of dispersion ED3 was about 1.1% by mass.
[0126]
[Table 1]

[0127]
[Table 2]

Claims (14)

Monomer as a) acrylic acid and _C 2 _{~C 12} - _40~80 wt% of at least one ester of an alkanol,
b) at least one vinyl aromatic monomer and / or methacrylic acid with _C 1 -C ₄ - at least one ester 10 to 40% by mass of alkanol,
c) 2-15% by weight of at least one monoester of C ₂ -C ₁₀ -alkanediol and acrylic acid or methacrylic acid,
d) have at least one acid group, alpha, beta-ethylenically unsaturated C ₃ -C 6 _- monocarboxylic acids and monoethylenically unsaturated C ₄ -C 8 _- is selected from among dicarboxylic acids 0.2 to 0.8% by weight of the ethylenically unsaturated monomer , or a salt thereof,
e) Dispersed in at least one aqueous phase containing less than 5% by weight of ethylenically unsaturated nitrile and f) less than 1% by weight of α, β ethylenically unsaturated monocarboxylic acid and dicarboxylic acid amide polymerized together. Of an ammonia-free aqueous polymer dispersion containing a modified copolymer as an admixture for inorganic building materials based on hydraulic binders.   Use according to claim 1, wherein the polymer dispersion comprises 0.2 to 10% by weight of at least one alkoxylated emulsifier, based on the copolymer.   Use according to claim 2, wherein a mixture of at least one nonionic alkoxylated emulsifier and at least one anionic emulsifier is used as the alkoxylated emulsifier. Alkoxylated nonionic emulsifier, nonionic ethoxylated with an average degree of ethoxylation of 2~150 _C 6 _{~C 32} - fatty _alcohols, C 6 _{-C 32} - oxo alcohols and _C 6 _{-C 32} - is selected from alkylphenol The use according to claim 3. Anionic emulsifiers, average ethoxylation _C 6 _{-C 32} having a degree of ethoxylation of from 2 to 150 - fatty alcohols, ethoxylated _C 6 _{-C 32} - oxo alcohols and ethoxylated _C 6 _{-C 32} - anionic alkylphenol Use according to claim 3 or 4, which is an alkoxylated anionic emulsifier selected from sulfuric acid-half esters and salts thereof. Copolymer having a glass transition temperature T _g below + 40 ° C., the use of any one of claims 1 to 5. A copolymer of 55 to 80% by weight of at least one monomer selected from a) ethyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate as monomers;
b) 12-35% by weight of styrene and / or methyl methacrylate,
_c) C 2 ~C ₆ - at least one monoester 3-9 wt% of alkane diols with acrylic acid or methacrylic acid, and <br/> d) acrylic acid, methacrylic acid, maleic acid and itaconic acid 0.2 to 8% by mass of at least one ethylenically unsaturated carboxylic acid selected from
7. Use according to any one of claims 1 to 6, comprising polymerized together.   8. Use according to any one of claims 1 to 7, wherein the polymer dispersion has a pH value in the range of 6.7 to 8.0.   Use according to claim 8, wherein the pH value is adjusted by the addition of at least one base selected from alkali metal hydroxides and alkaline earth metal hydroxides.   For inorganic building materials based on hydraulic binders of polymer powders or polymer granules obtained by removal of at least 80% by weight of volatile constituents from the polymer dispersion according to any one of claims 1 to 9 Use as an admixture.   Use according to any one of claims 1 to 10, wherein the copolymer is used in an amount of 5 to 250% by weight, based on the dry weight of the hydraulic binder.   12. Use according to any one of claims 1 to 11, wherein the hydraulic binder is cement.   The aqueous polymer dispersion according to any one of claims 1 to 9 and / or the at least one copolymer in the form of polymer powder or polymer granule according to claim 10 with respect to the dry mass of the inorganic component. An inorganic building material based on a hydraulic binder containing 0.5 to 150% by weight. In a method for improving the mechanical strength, elasticity and processability of building materials based on hydraulic binders,
At least one hydraulic binder,
-At least one aqueous polymer dispersion according to any one of claims 1 to 9 and / or polymer powder or polymer granules according to claim 10 and optionally-water and / or additives mixed together how to.